阅读说明：本技术 碱可膨胀的多功能流变改性剂 (Alkali-swellable multifunctional rheology modifier ) 是由 M·M·范德胡夫 K·A·罗德古斯 S·潘塔 A·J·拜莱 D·C·瓦蒂洛 于 2018-11-16 设计创作，主要内容包括：本发明涉及包含核-壳聚合物的碱可膨胀的流变改性剂,该核-壳聚合物包含核聚合物及含至少一个壳共聚物层的壳,至少一个壳共聚物层为至少部分交联的且含有摩尔百分比高于该核聚合物中交联剂的摩尔百分比的交联剂,其限制条件为,若该核聚合物中交联剂的摩尔百分比为零,则该核聚合物占该核-壳聚合物超过60wt％；和/或该核聚合物包含至少一种缔合单体；和/或至少一种壳共聚物层共聚物包含至少一种缔合单体；和/或以不计入该交联剂的该壳共聚物中单体的摩尔量计,该至少部分交联的至少一个壳共聚物层包含超过3mol％交联剂。包含该碱可膨胀的流变改性剂的水性组合物包括个人护理配制剂、医疗保健用配制剂、农用配制剂、油漆配制剂、涂料配制剂、衣物及织物护理配制剂、家用清洁配制剂以及工业及机构用清洁配制剂。(The invention relates to an alkali-swellable rheology modifier comprising a core-shell polymer, the core-shell polymer comprising a core polymer and a shell comprising at least one shell copolymer layer, the at least one shell copolymer layer being at least partially crosslinked and containing a crosslinking agent in a higher molar percentage than the molar percentage of the crosslinking agent in the core polymer, with the proviso that if the molar percentage of the crosslinking agent in the core polymer is zero, the core polymer comprises more than 60 wt% of the core-shell polymer; and/or the core polymer comprises at least one associative monomer; and/or at least one shell copolymer layer copolymer comprises at least one associative monomer; and/or the at least one at least partially crosslinked shell copolymer layer comprises more than 3 mol% of crosslinking agent, based on the molar amount of monomers in the shell copolymer not counting into the crosslinking agent. Aqueous compositions comprising the alkali-swellable rheology modifier include personal care formulations, healthcare formulations, agricultural formulations, paint formulations, coating formulations, laundry and fabric care formulations, household cleaning formulations, and industrial and institutional cleaning formulations.)

1. An alkali-swellable rheology modifier comprising a core-shell polymer comprising a core polymer and a shell comprising at least one shell copolymer layer, wherein the core polymer and the at least one shell copolymer layer are each polymerized from a monomer mixture comprising a) one or more anionic ethylenically unsaturated monomers; and b) one or more hydrophobic ethylenically unsaturated monomers; the anionic ethylenically unsaturated monomer is present in the core polymer or at least one of the shell polymer layers at more than 10 mol%; at least one of the shell copolymer layers is at least partially crosslinked and contains a crosslinking monomer in a mole percent greater than the mole percent of the crosslinking monomer in the core polymer,

with the proviso that if the mole percentage of crosslinking monomer in the core polymer is zero, the core-shell polymer is characterized by at least one of:

(i) the core polymer comprises more than 60 wt% of the core-shell polymer;

(ii) the core polymer comprises at least one associative monomer;

(iii) at least one shell copolymer layer comprises at least one associative monomer; or

(iv) The at least one shell copolymer layer that is at least partially crosslinked comprises more than 3 mol% crosslinking monomer, based on the total molar amount of monomers in the at least one shell copolymer layer not counting crosslinking agent.

2. The alkali-swellable rheology modifier of claim 1, wherein the core polymer and the at least one shell copolymer layer are each polymerized from a monomer mixture comprising a) one or more anionic ethylenically unsaturated monomers; b) one or more hydrophobic ethylenically unsaturated monomers; and further comprising one or more monomers selected from the group consisting of nonionic ethylenically unsaturated monomers and associative monomers.

3. An alkali-swellable rheology modifier as claimed in claim 1 or 2, wherein the core contains 0 mol% of cross-linking monomer and the core comprises more than 60 wt% of the core-shell polymer.

4. The alkali-swellable rheology modifier of any of claims 1 to 3, wherein the core contains 0 mol% of a crosslinking monomer and the core comprises an associative monomer.

5. The alkali-swellable rheology modifier of any of claims 1 to 4, wherein the core contains 0 mol% crosslinking monomer and at least one of the shell copolymer layers comprises associative monomer.

6. The alkali-swellable rheology modifier of any of claims 1 to 5, wherein the core contains 0 mol% crosslinking monomer and at least one of the shell copolymer layers contains more than 3 mol% crosslinking monomer based on the mol of monomer in the shell copolymer layer not counting into the crosslinking agent.

7. The alkali-swellable rheology modifier of claim 1, wherein said core polymer comprises at least 0.01 mol% crosslinking monomer.

8. An alkali-swellable rheology modifier according to any of claims 2-7, wherein said one or more anionic ethylenically unsaturated monomers are selected from the group consisting of acrylic acid, methacrylic acid, 2-ethacrylic acid, α -chloro-acrylic acid, α -cyanoacrylic acid, β -methyl-acrylic acid (crotonic acid), α -phenylacrylic acid, β -acryloxypropionic acid, sorbic acid, α -chlorosorbic acid, angelic acid, 2-carboxyethyl (meth) acrylate, cinnamic acid, p-chlorocinnamic acid, β -styrylacrylic acid (1-carboxy-4-phenyl-1, 3-butadiene), itaconic acid, maleic acid, citraconic acid, methylfumaric acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxyethylene, muconic acid, 2-acryloxypropionic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, sodium methallylsulfonate, sulfonated styrene, allyloxybenzenesulfonic acid, and vinylphosphonic acid, and combinations thereof.

9. The alkali-swellable rheology modifier of any of claims 2 to 8, wherein the one or more hydrophobic ethylenically unsaturated monomers are selected from: c of acrylic acid and methacrylic acid₁-C₃₂An alkyl ester; c of acrylic acid and methacrylic acid₄-C₃₂Alkylamides, benzyl (meth) acrylate, phenyl (meth) acrylate, ethoxylated benzyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and 10-hydroxydecyl (meth) acrylate, styrene, α -methylstyrene, vinyltoluene, tert-butylstyrene, isopropylstyrene and p-chlorostyrene, vinyl acetate, vinyl butyrate, vinyl heptanoate, vinyl valerate, vinyl hexanoate, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl laurate, vinyl caprolactam, (meth) acrylonitrileIsobutylene, isoprene, vinyl chloride, vinylidene chloride, 1-allylnaphthalene, 2-allylnaphthalene, 1-vinylnaphthalene, 2-vinylnaphthalene, and combinations thereof.

10. The alkali-swellable rheology modifier of any of claims 2 to 9, wherein the one or more nonionic ethylenically unsaturated monomers are selected from: acrylamide, methacrylamide, N-C₁-C₃Alkyl (meth) acrylamides, N-C₁-C₃Dialkyl (meth) acrylamides, C of (meth) acrylic acid₁To C₄Hydroxyalkyl esters, vinyl morpholine, vinyl pyrrolidone, vinyl propionate, vinyl butyrate, and (poly) C₁-C₄Alkoxylated (meth) acrylates such as poly (ethylene glycol)_n(meth) acrylate and poly (propylene glycol)_n(meth) acrylates (wherein n ═ 1 to 100, preferably 3 to 50 and most preferably 5 to 20); ethoxylation C₁-C₄Alkyl radical, C₁-C₄Alkylaryl or aryl monomers such as methoxypolyethylene glycol (meth) acrylate, allyl glycidyl ether, allyl alcohol and glycerol (meth) acrylate; and combinations thereof.

11. The alkali-swellable rheology modifier of any of claims 1 to 10, further comprising a spray-drying aid.

12. The alkali-swellable rheology modifier of any of claims 1 to 11, in the form of an emulsion.

13. The alkali-swellable rheology modifier of any of claims 1 to 11, in the form of a dry powder.

14. An aqueous composition comprising the alkali-swellable rheology modifier of any of claims 1-13.

15. The aqueous composition of claim 14, wherein the composition is selected from the group consisting of: personal care formulations, agricultural formulations, paint formulations, coating formulations, laundry and fabric care formulations, household cleaning formulations and cleaning formulations for industry and institutional use, and formulations for use in the electronics component industry, and formulations for use in the construction industry.

Technical Field

In one aspect, the present application relates to a rheology modifier comprising an alkali swellable core-shell polymer comprising a core and at least one crosslinked shell layer, wherein the mole percentage of crosslinking agent in the at least one crosslinked shell layer is greater than the mole percentage of crosslinking agent in the core. In another aspect, the present application relates to such base-swellable core-shell polymeric rheology modifiers suitable for use in aqueous systems, and which provide other functions useful in the final formulation. Further, the present application relates to the formation of rheology-stable and phase-stable aqueous surfactant compositions comprising such alkali-swellable core-shell polymers.

Background

Rheology modifiers, also known as thickeners or tackifiers, are ubiquitous in a variety of commercial formulations, such as personal care formulations, healthcare formulations, agricultural formulations, paint formulations, coating formulations, laundry and fabric care formulations, household cleaning formulations, and industrial and institutional cleaning formulations. Rheology modifiers can be selected for particular formulations to provide rheological properties for particular purposes. For example, for personal care formulations, rheology modifiers may be selected for their ability to provide viscosity and flow characteristics, lathering, spreadability, clarity, sensory impact, and mildness.

Carbomers (carbomers) are a class of thickeners known in the art of personal care formulations. Carbomers, as synthetic polymers based on acrylic monomers, are usually supplied in powder form.

In personal care hair styling compositions, a thickening agent such as a carbomer is often used in combination with another polymer that forms a film on the hair to act as a hair fixative. Carbomers are generally incompatible with ionic polymers, and therefore, other fixative polymers used in combination with carbomers are generally non-ionic. One such nonionic fixative polymer commonly used with carbomers is polyvinylpyrrolidone. Although other fixative polymers, particularly anionic polymers, are known to be more effective hair fixatives than polyvinylpyrrolidone, these other fixative polymers have limited compatibility with carbomers. Thus, the use of carbomer rheology modifiers may impose significant limitations on the selection of other hair fixative polymers and other ingredients that may be incorporated into a personal care formulation by a personal care formulator.

Carbomer powders can also be difficult to incorporate into personal care formulations. During processing, carbomer powder becomes electrostatically charged as a result of transfer into and out of the container and tends to adhere to oppositely charged surfaces, including atmospheric dust, requiring specialized dusting equipment. Powdered materials may also agglomerate during the rehydration procedure, creating "fish eyes" that may be difficult to completely disperse and may remain in the finished product. This means that the preparation of aqueous dispersions is rather cumbersome, energy-intensive and time-consuming, unless special precautions and expensive equipment are employed. Formulators of compositions containing thickened surfactant ingredients wish to be able to formulate their products at ambient temperature (cold processing). Thus, for some formulations, it is desirable to provide rheology modifier compositions in liquid form, or in powder form that are more easily dispersible and less prone to dusting than carbomer powders.

To avoid these problems of the prior art, there is a need for rheology modifiers that are easy to use, provide desirable rheology characteristics, and have good solubility. For some formulations, it is also desirable to have rheology modifiers that provide good clarity. In addition, there is a need for rheology modifiers that provide these qualities and further provide hair fixative functionality to reduce or eliminate the need for additional fixative components in hair fixative personal care compositions where the rheology modifiers are present. It is also desirable that such rheology modifiers provide these qualities over a pH range of at least about 4.5-9. Still further, it is desirable that at least a portion of the rheology is derived from natural renewable resources.

Summary of The Invention

In one aspect, the present application relates to an alkali-swellable rheology modifier suitable for use in an aqueous composition, the alkali-swellable rheology modifier comprising at least one core-shell polymer comprising a core polymer and a shell comprising at least one shell copolymer layer, wherein the at least one shell copolymer layer is an at least partially crosslinked copolymer comprising a greater mole percent of a crosslinking agent than the mole percent of the crosslinking agent in the core polymer, with the proviso that if the mole percent of the crosslinking agent in the core polymer is zero, the core-shell polymer is characterized by at least one of: (a) the core polymer comprises more than 60% by weight of the core-shell polymer; (b) the core polymer comprises at least one associative monomer; (c) at least one shell copolymer layer comprises at least one associative monomer; or (d) the monomers in the at least one at least partially crosslinked shell copolymer layer comprise more than 3 mol% crosslinking monomer, based on the molar amount of monomers in the at least one shell copolymer layer, not counting the crosslinking agent.

The present application further relates to aqueous compositions comprising such alkali-swellable rheology modifiers.

In one aspect, the weight ratio of shell to core and the amount of respective crosslinkers for the shell and core are selected to provide preferred rheological characteristics in a particular end use application.

The core polymer and the at least one shell copolymer layer are each polymerized from a monomer composition comprising a) one or more anionic ethylenically unsaturated monomers; b) one or more hydrophobic ethylenically unsaturated monomers; c) optionally one or more nonionic ethylenically unsaturated monomers; and d) optionally one or more associative monomers. At least one of the shell copolymer layers further comprises one or more crosslinking agents. The core polymer optionally may include one or more cross-linking agents.

In one aspect, the alkali-swellable rheology modifier comprises a core-shell polymer, wherein the core polymer contains 0 mol% crosslinker, and the core polymer comprises more than 60 wt% of the core-shell polymer.

In one aspect, the alkali-swellable rheology modifier comprises a core-shell polymer, wherein the core polymer contains 0 mol% crosslinker, and the core polymer comprises an associative monomer.

In one aspect, the alkali-swellable rheology modifier comprises a core-shell polymer, wherein the core polymer contains 0 mol% crosslinker, and at least one shell copolymer layer comprises associative monomers.

In one aspect, the alkali-swellable rheology modifier comprises a core-shell polymer, wherein the core polymer contains 0 mol% crosslinker, and at least one shell copolymer layer comprises more than 3 mol% crosslinker, based on the moles of monomers in the shell copolymer layer not counting the crosslinker.

In one aspect, the alkali-swellable rheology modifier comprises a core-shell polymer, wherein the core polymer contains at least 0.01 mol% crosslinker.

In one aspect, the alkali-swellable rheology modifier comprises a core-shell polymer, wherein the core polymer contains at least 0.01 mol% crosslinker, and the core comprises more than 60 wt% of the core-shell polymer.

In one aspect, the alkali-swellable rheology modifier comprises a core-shell polymer, wherein the core polymer contains at least 0.01 mol% crosslinker, and the core polymer comprises an associative monomer.

In one aspect, the alkali-swellable rheology modifier comprises a core-shell polymer, wherein the core polymer contains at least 0.01 mol% crosslinker, and at least one shell copolymer layer comprises an associative monomer.

In one aspect, the alkali-swellable rheology modifier comprises a core-shell polymer, wherein the core contains at least 0.01 mol% crosslinker, and at least one shell copolymer layer comprises more than 3 mol% crosslinker, based on the moles of monomer in the shell copolymer layer not counting the crosslinker.

In some embodiments, the alkali-swellable rheology modifier comprises C (meth) acrylic acid₁-C₆Core-shell polymers of alkyl ester monomers. In some embodiments, the core-shell polymer includes at least one acrylic acid C₁-C₆Alkyl ester monomer and at least one methacrylic acid C₁-C₆An alkyl ester monomer.

In another aspect, the present application relates to alkali-swellable rheology modifiers comprising a core-shell polymer and further comprising a spray-drying aid.

In another aspect, the present application relates to an alkali-swellable rheology modifier comprising a core-shell polymer and further comprising a spray-drying aid derived from a natural renewable resource.

In one embodiment, the natural renewable resource from which the spray drying adjuvant is derived is a polysaccharide.

In one embodiment, the natural renewable resource that is the source of the spray drying aid is cellulose based.

In one embodiment, the natural renewable resource from which the spray drying adjuvant is derived is based on starch.

In another aspect, the present application relates to an alkali-swellable rheology modifier comprising a core-shell polymer and further comprising a spray-drying aid derived from a polyvinyl acetate derivative.

In one embodiment, a method of making an alkali-swellable rheology modifier composition comprises the steps of: (i) providing a base-swellable core-shell polymer as disclosed herein; (ii) co-mixing the core-shell polymer with a spray drying aid; and (iii) drying the blend; wherein the alkali-swellable rheology modifier is in the form of a dry powder.

In another aspect, the present application relates to an aqueous polymer emulsion comprising an alkali swellable core-shell polymer as described herein.

In another aspect, the present application relates to formulations comprising an alkali-swellable rheology modifier as disclosed herein.

In one embodiment, the formulation comprising the alkali-swellable rheology modifier as disclosed herein is selected from the group consisting of personal care formulations, healthcare formulations, agricultural formulations, paint formulations, coating formulations, laundry and fabric care formulations, household cleaning formulations, and industrial and institutional cleaning formulations, and formulations used in the electronic component industry and formulations used in the construction industry.

In one embodiment, the formulation is an aqueous formulation further comprising one or more surfactants. The surfactant may be selected from any of anionic, cationic, amphoteric and nonionic surfactants, and mixtures thereof.

In one embodiment, the formulation is a personal care formulation.

In one embodiment, the personal care formulation is a hair fixative formulation, and the alkali-swellable rheology modifier additionally provides a film forming function such that the rheology modifier also serves as a hair fixative ingredient in the formulation.

Brief description of the drawings

Fig. 1 is a graph of the percent curl retention as a function of time in the high humidity curl retention evaluation for the hair gel formulations of examples 71-74, evaluated as described in example 82.

Fig. 2 is a graph of the percent curl retention as a function of time in the high humidity curl retention evaluation for the hair gel formulations of examples 75-78, evaluated as described in example 82.

Detailed Description

Exemplary embodiments according to the present application will be described. Various modifications, adaptations, or variations of the exemplary embodiments described herein may become apparent to those skilled in the art when disclosing the exemplary embodiments. It is to be understood that all such improvements, modifications, or changes that rely on the teachings of the present application are deemed to be within the scope and spirit of the present application and, through such improvements, modifications, or changes, these teachings motivate the art.

The polymers and compositions disclosed herein may suitably comprise, consist of, or consist essentially of the components, elements, and process descriptions described herein. The embodiments illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein.

In the context of the present invention, the term "(co) polymer" denotes a polymer or a copolymer. The term "polymer" is used interchangeably herein with the term "copolymer".

As used herein and throughout this specification, the terms "core-shell morphology", "core-shell structure", "core-shell polymer", "segmented core-shell polymer" and "two-stage polymer" or "multi-stage polymer" are used interchangeably and mean polymer particles prepared by a sequential or staged polymerization procedure in which monomer repeat units of each sequence or stage are added to a polymerization reactor and begin undergoing polymerization, followed by the initiation of the addition of repeat units of subsequent sequences or stages and polymerization. In some embodiments, the polymerization reaction of one stage will be substantially complete before the monomer of the next stage is added to the polymerization reactor; in some embodiments, the polymerization reaction of one stage may be only partially completed before the monomer of the next stage is added to the polymerization reactor. As most preferably understood, in the structures of these core-shell polymers disclosed herein, the polymers forming the core portion, sequence or stage and the polymers forming the shell portion, sequence or stage are physically and/or chemically bonded and/or attracted to each other. The structure and/or chemical composition (e.g., monomer composition and/or amount) of the disclosed copolymer particles varies from the interior to the exterior of the particle and, thus, the gradient regions may also have different physical and chemical properties. These changes can be gradual in nature, producing a morphology with a gradient in polymer structure or composition along any radius thereof. Alternatively, the change in polymer structure or composition may be determined relatively preferentially as one moves along the radius of the particle from the center outwards, resulting in a morphology having relatively different core portions with one polymer composition and relatively different shell portions with a different polymer composition. The segmented core-shell morphology may comprise multiple layers or zones having different polymer compositions, so long as at least one of the shell copolymer layers is an at least partially crosslinked polymer containing a higher mole percent of crosslinking agent than the mole percent of crosslinking agent in the core polymer. The rate of change of the polymer morphology of the particles is not particularly important so long as the polymer exhibits the requisite characteristics described herein. Thus, as used herein, the terms "core" and "shell" refer to the polymeric material inside and outside of the particle, respectively, and the use of the terms should not be construed to mean that the disclosed polymer particles must exhibit a distinct interface between the polymers inside and outside of the particle.

In some embodiments, the segmented core-shell polymer particles can be in the form of a core portion completely coating a shell portion or being encapsulated within a shell portion. In other embodiments, the core-shell polymer particles may be in a form in which the core portion is only partially coated or encapsulated. It is also understood that in describing the "core polymer" and "shell polymer" of the disclosed segmented core-shell polymers, there can be a substantial amount of polymer interpenetration in the core and shell of the polymer particles. Thus, the "core polymer" may extend to some extent into the shell of the particle, forming a region in the shell particle, and vice versa.

The terms "core polymer" and "shell polymer" and similar terms are used herein to describe the polymeric material in this named part of the polymer particle in a conventional manner without attempting to identify any particular polymer as being absolutely "shell" or absolutely "core" polymer.

As used herein, the term "(meth) acrylic" is intended to include both acrylic and methacrylic. Similarly, as used herein, the term "alkyl (meth) acrylate" is intended to include alkyl acrylates and alkyl methacrylates.

The term "aqueous" as used in the formulation or medium means that water is present in an amount sufficient to at least swell or dissolve the multi-purpose polymer in a composition formulated with the polymer.

The alkali-swellable core-shell polymers of the invention impart desirable rheological properties to aqueous formulations having a pH in the range of 2 to 12, or in the range of 3 to 10, or in the range of 4.5 to 10, selected from personal care formulations, healthcare formulations, agricultural formulations, paint formulations, coating formulations, laundry and fabric care formulations, home care formulations, and industrial and institutional care formulations, and formulations for use in the electronics component industry and formulations for use in the construction industry. The alkali-swellable core-shell polymers of the present invention can be used in aqueous systems and in compositions containing one or more surfactants (e.g., anionic, cationic, amphoteric, nonionic surfactants, and/or combinations of any two or more thereof). In some embodiments, the alkali swellable core-shell polymer may also provide hairstyling efficacy when used in a personal care formulation as a hairstyling formulation. In some embodiments, the alkali swellable core-shell polymer is a useful thickener in products containing active acid components and is a useful thickener and emulsifier for emulsions (creams, lotions). In some embodiments, the alkali swellable core-shell polymer is a useful film former, coating aid, and deposition aid in addition to thickening for products containing surfactants, colorants, hair and skin conditioning agents, silicones, mono-quaternary ammonium compounds, polyquaternary ammonium compounds, antidandruff agents, anti-aging compounds, anti-wrinkle compounds, anti-pigment compounds, anti-cellulite compounds, anti-acne compounds, vitamins, analgesics, anti-inflammatory compounds, self-tanning agents, hair growth promoters, UV protectants, skin lightening agents, vegetable, plant and botanical extracts, antiperspirants, antioxidants, deodorants, hair fixative polymers, emollient oils, and combinations thereof.

In some preferred embodiments, the alkali-swellable core-shell polymers disclosed herein also impart desirable clarity characteristics, measured in units of turbidity, in addition to the desired rheological characteristics as described above. An aqueous composition with a rheology modifier disclosed herein can have a haze value of ≦ 1000NTU in one aspect, a haze value of ≦ 500NTU in another aspect, a haze value of ≦ 200NTU in another aspect, 100NTU in another aspect, and a pH value of ≦ 50NTU in another aspect, as measured in a thickened aqueous polymer composition comprising about 2 wt% polymer (active polymer solids) and the balance water, and wherein the thickened composition has a pH value of about 7.

As used herein, the term "rheological property" and grammatical variations include, but are not limited to, properties such as: viscosity, i.e., the viscosity increases or decreases in response to shear stress, and flow characteristics; gelling properties, such as stiffness, elasticity, fluidity, and the like; foaming characteristics such as foam stability, foam density, peak holding ability, and the like; suspension characteristics, such as yield value; as well as aerosol characteristics such as the ability to form aerosol droplets when dispensed from a self-propelled dosage form or a mechanical pump type aerosol dispenser; a liquid flow rate through the pump dispenser; or any mass or property that can be measured with a viscometer or a rotational or extensional rheometer. In some preferred embodiments, the aqueous compositions with rheology modifiers disclosed herein will have yield values sufficient to support the suspension of aesthetic and cosmetic pharmaceutical beads and particles, air bubbles, exfoliants, and the like.

When used in a composition, the term "aesthetic property" and grammatical variations thereof refers to visual and tactile psychosensory product properties such as color, clarity, smoothness, tackiness, lubricity, texture, conditioning and feel, and the like.

Here, as well as elsewhere in the specification and claims, individual values (including carbon atom values) or limits may be combined to form additional unpublished and/or unpublished ranges.

The headings provided herein are for illustration and are not intended to limit the present application in any way or manner.

Core-shell polymers

An alkali-swellable rheology modifier for use in an aqueous composition comprises a core-shell polymer, the shell comprising one or more copolymer layers, wherein at least one shell copolymer layer is an at least partially crosslinked polymer comprising a higher mole percentage of a crosslinking agent than the mole percentage of the crosslinking agent in the core polymer, with the proviso that if the mole percentage of the crosslinking agent in the core is zero, (a) the core comprises more than 60 wt% of the core-shell polymer, and/or (b) the core comprises an associative monomer, and/or (c) at least one shell copolymer layer comprises an associative monomer, and/or (d) the at least partially crosslinked at least one shell copolymer layer comprises more than 3 mol% of the crosslinking agent, based on the moles of monomer in the shell copolymer layer, exclusive of the crosslinking agent. The core-shell polymer may include a plurality of shell copolymer layers, which may be the same or different from one another in the type and ratio of monomers in the polymer backbone as the core layer. The plurality of shell copolymer layers may have any mole percent of crosslinking agent, so long as the core (first stage) polymer has a lower mole percent of crosslinking agent than at least one of the crosslinked shell copolymer layer (subsequent stage) copolymers.

In one aspect, the core-shell polymer comprises from about 1 wt% to about 95 wt% of the one or more shell copolymer layers, based on the total weight of the core-shell polymer. In one embodiment, the core-shell polymer comprises from about 5 wt% to about 60 wt% of the one or more shell copolymer layers, in one embodiment from about 10 wt% to about 40 wt% of the one or more shell copolymer layers, and in one embodiment from about 15 wt% to about 35 wt% of the one or more shell copolymer layers, in each case based on the total weight of the core-shell polymer, with the remainder of the polymer being the core polymer. In one embodiment, if the core polymer comprises zero cross-linking agent and no associative monomer is present in any core or shell copolymer layer, the core comprises more than 60 wt% and up to 95 wt% of the core-shell polymer.

Monomer component

The core polymer is polymerized from a monomer composition comprising a) one or more non-associative anionic ethylenically unsaturated monomers; b) one or more hydrophobic ethylenically unsaturated monomers; c) optionally one or more nonionic ethylenically unsaturated monomers; d) optionally one or more cross-linking agents; and e) optionally one or more cross-linking agents. The one or more shell copolymer layers are each polymerized from a monomer composition comprising a) one or more non-associative anionic ethylenically unsaturated monomers; b) one or more hydrophobic ethylenically unsaturated monomers; c) optionally one or more nonionic ethylenically unsaturated monomers; d) optionally one or more associative monomers; and e) optionally one or more crosslinking agents, provided that at least one of the shell copolymer layers comprises one or more crosslinking agents. The one or more crosslinking agents will be present in the monomer composition of the at least one shell copolymer layer, and will optionally be present in the core monomer composition, as long as the crosslinking agent present in the at least one shell copolymer layer is greater than the crosslinking agent in the core polymer.

Anionic monomer

As used herein, the term "anionic ethylenically unsaturated monomer" means an ethylenically unsaturated monomer capable of producing a negative charge when the polymer is in aqueous solution, and the anionic monomer is not an associative monomer as defined below, these anionic ethylenically unsaturated monomers may include, but are not limited to, acrylic acid, methacrylic acid, 2-ethacrylic acid, α -chloro-acrylic acid, α -cyanoacrylic acid, β -methyl-acrylic acid (crotonic acid), α -phenylacrylic acid, β -acryloxypropionic acid, sorbic acid, α -chlorosorbic acid, angelic acid, 2-carboxyethyl (meth) acrylate, cinnamic acid, p-chlorocinnamic acid, β -styrylacrylic acid (1-carboxy-4-phenyl-1, 3-butadiene), itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxyethylene, muconic acid, 2-acryloxypropionic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, sodium methallylsulfonate, sulfonated styrene, allyloxybenzenesulfonic acid, and vinylphosphonic acid.

In one aspect, the amount of anionic ethylenically unsaturated monomer described under first monomer component a) is in the range of from about 10 mol% to about 90 mol%, in another aspect in the range of from about 20 mol% to about 80 mol%, and in the range of from about 30 mol% to about 70 mol%, or in yet another aspect more than 10 mol%, or at least 15 mol%, or at least 20 mol%, or at least 30 mol%, or at least 40 mol%, or at least 50 mol%, in each case the mol% being based on the total molar amount of monomers present in the stage not including the crosslinking agent, in the core polymer or shell copolymer layer using anionic ethylenically unsaturated monomers.

Hydrophobic monomers

As used herein, the term "hydrophobic ethylenically unsaturated monomer" means a monomer that is hydrophobic and capable of forming an emulsion system when reacted with a cationic ethylenically unsaturated monomer. For the purposes of this application, the hydrophobic ethylenically unsaturated monomer may be sparingly soluble in water, and has a water solubility of less than 6 grams per 100ml of water at 25 ℃, or less than 3 grams per 100ml of water at 25 ℃, preferably less than 2 grams per 100ml of water at 25 ℃, and most preferably less than 1.6 grams per 100ml of water at 25 ℃. These hydrophobic monomers may contain straight or branched alk (en) yl, cycloalkyl, aryl or alk (en) aryl moieties. Suitable hydrophobic ethylenically unsaturated monomers include C of acrylic acid and methacrylic acid₁-C₃₂Alkyl esters including methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tertiary amine (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl,Phenyl (meth) acrylate, ethoxylated benzyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 10-hydroxydecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-butyloctyl (meth) acrylate, 2-hexyldecyl (meth) acrylate, 2-octyldodecyl (meth) acrylate, 2-decyltetradecyl (meth) acrylate, 2-dodecylhexadecyl (meth) acrylate, behenyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; and C of acrylic acid and methacrylic acid₄-C₃₂Other suitable hydrophobic monomers include styrene, α -methylstyrene, vinyltoluene, tert-butylstyrene, isopropylstyrene and p-chlorostyrene, vinyl acetate, vinyl butyrate, vinyl heptanoate, vinyl valerate, vinyl hexanoate, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl laurate, vinyl caprolactam, (meth) acrylonitrile, butadiene, isobutylene, isoprene, vinyl chloride, vinylidene chloride, 1-allylnaphthalene, 2-allylnaphthalene, 1-vinylnaphthalene, 2-vinylnaphthalene.

Preferably ethyl (meth) acrylate, methyl (meth) acrylate, 2-ethylhexyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary amine (meth) acrylate, vinyl acetate, t-butylacrylamide and combinations thereof. In one embodiment, ethyl acrylate, methyl methacrylate, vinyl acetate, butyl acrylate, and combinations thereof are preferred.

Exemplary alkyl (meth) acrylate monomers under monomer component b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary amine (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, and mixtures thereof. In one embodiment, ethyl acrylate is preferred.

In one aspect, the hydrophobic ethylenically unsaturated monomer described under second monomer component b) is used in an amount ranging from about 10 to about 90 mol%, in another aspect from about 20 to about 80 mol%, and in yet another aspect from about 30 to about 70 mol%, or in yet another aspect at least 10 mol%, or at least 15 mol%, or at least 20 mol%, or at least 30 mol%, or at least 40 mol%, or at least 50 mol%, in each case mol% based on the total molar amount of monomers present in the stage not including the crosslinking agent, in the core polymer or shell copolymer layer using the hydrophobic ethylenically unsaturated monomer. In one embodiment, the hydrophobic ethylenically unsaturated monomer is present in 20 to 30 mol%, based on the total molar amount of monomers present in the stage excluding the crosslinking agent.

Optionally non-ionic ethylenically unsaturated monomers

As used herein, the term "nonionic ethylenically unsaturated monomer" means an ethylenically unsaturated monomer that does not introduce a charge in the core-shell polymer, and which is neither a hydrophobic ethylenically unsaturated monomer, nor an associative monomer, nor a cross-linking agent (each as defined herein). These nonionic ethylenically unsaturated monomers include, but are not limited to, acrylamide, methacrylamide, N-C₁-C₃Alkyl (meth) acrylamides and N, N-C₁-C₃Dialkyl (meth) acrylamides, such as N-methylmethacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-dimethylacrylamide and N, N-dimethylmethacrylamide; vinyl morpholine, vinyl pyrrolidone, vinyl propionate, vinyl butyrate, ethoxylated alkyl, alkaryl or aryl monomers, e.g. methoxypolyethylene glycol (meth) acrylate, allyl glycidyl ether, allyl alcohol, glycerol (meth) acrylate, C (meth) acrylate₁To C₄Hydroxyalkyl esters, and the like. The nonionic ethylenically unsaturated monomer includes (poly) C₁-C₄Alkoxylated (meth) acrylates, e.g. poly (ethylene glycol)_n(meth) acrylate and poly (propylene glycol)_n(meth) acrylates wherein n ═ 1 to 100, preferably 3 to 50, and most preferably 5 to 20; ethoxylation C₁-C₄Alkyl radical, C₁-C₄An alkaryl or aryl monomer. In one aspect, the optional nonionic ethylenically unsaturated monomer component c) is methoxypolyethylene glycol (meth) acrylate. The nonionic monomers can be used in any combination.

Optional (meth) acrylic acid C₁To C₄Hydroxyalkyl esters may include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and (butanediol mono (meth) acrylate). In one aspect, the hydroxyalkyl ester of component c) is selected from 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate.

In one aspect, the optional nonionic ethylenically unsaturated monomer, when present, is present in a range of from about 10 to 90 mol%, in another aspect in a range of from about 20 to about 80 mol%, and in another aspect in an amount in a range of from about 30 to about 70 mol%, based in each case on the total molar amount of monomers present in the stage that does not include a crosslinking agent, based on monomers present in the core polymer or shell copolymer layer using the optional nonionic ethylenically unsaturated monomer.

Associative monomers

As used herein, the term associative monomer is intended to mean an ethylenically unsaturated monomer containing a hydrophobe and a spacer moiety that displaces the hydrophobe sufficiently far from the polymer backbone to form a hydrophobic association in aqueous solution, and wherein the hydrophobe comprises at least six carbon atoms. The spacer moiety is typically an ethoxylate group, but any other group that extends the hydrophobe away from the polymer backbone may be used. Hydrophobes bearing spacer moieties include, but are not limited to, alcohol ethoxylates, alkyl phenoxy ethoxylates, propoxylated/butoxylated ethoxylates, ethoxylated polysiloxanes, and the like. In one embodiment, the composition is preferablySelected hydrophobes with spacer moieties include alcohol ethoxylates and/or alkyl phenoxy ethoxylates. In another embodiment, alcohols having a carbon chain length of 6 to 40 and 6 to 100 moles of ethoxylated alcohol ethoxylate are more preferred. In a further embodiment, alcohol ethoxylates containing alcohols with a carbon chain length of from 12 to 22 and from 15 to 30mol of ethoxylation are particularly preferred. The hydrophobe may be a linear or branched alk (en) yl, cycloalkyl, aryl, alk (en) aryl or alkoxylated derivative. In one embodiment, most preferably the hydrophobes are straight or branched chain alcohols containing 12 to 32 carbons and amines. The associative monomer may contain an ethylenically unsaturated monomer covalently linked to the hydrophobe. In one embodiment, the ethylenically unsaturated monomer portion of the associative monomer is preferably a (meth) acrylate, itaconate, and/or maleate ester containing an ester linking group. However, the associative monomer may also contain amide, urea, carbamate, ether, alkyl, aryl, and other suitable linking groups. The hydrophobe may be an alkylamine or dialkylamine ethoxylate. In one embodiment, (meth) acrylate groups are most preferred. In another embodiment, it is preferred that the associative monomer is C_12-32(EO)_10-30Methyl (acrylate), or C_12-32(EO)_10-30Itaconate ester, or C_12-32(EO)_10-30Maleic acid ester.

In one embodiment, the associative monomer has the structure of formula (I)

Wherein

R₁Is selected from-H, -CH₃-COOH or-CH₂COOH；

A is selected from-CH₂C(O)O-、-C(O)O-、-O-、-CH₂O-、-CH₂C(O)N-、-C(O)N-、-CH₂-、-O-C(O)-、-NHC(O)O-、-NHC(O)NH-、-C₆H₄(R₅)-NH-C(O)-O-、-C₆H₄(R₅)-NH-C(O)-NH-、-C(O)O-CH₂-CH(CH₂OH)-O-、-C(O)O-CH₂-CH(CH₂OH)-NH-、-C(O)O-CH₂-CH-CH₂(OH)-O-、-C(O)O-CH₂-CH-CH₂(OH)-NH-、-CH₂-O-CH₂-CH(CH₂OH)-O-、-CH₂-O-CH₂-CH-CH₂(OH)-O-、-CH₂-O-CH₂-CH(CH₂OH) -NH-or-CH₂-O-CH₂-CH-CH₂(OH)-NH-；

(R₃-O)_nIs a polyoxyalkylene radical which is of formula C₂To C₄Homopolymers, random copolymers or block copolymers of oxyalkylene units, in which each R is₃Is independently selected from-C₂H₄-、-C₃H₆-、-C₄H₈-or mixtures thereof, and n is an integer in the range of about 5 to about 250, preferably n is 5-100, more preferably 10-50 and most preferably 15-30;

R₄is C₆-C₃₆A linear or branched, saturated or unsaturated alk (en) yl or alk (en) aryl group, preferably C₈-C₃₂Straight-chain or branched alk (en) yl, more preferably C₁₀-C₂₂Straight-chain alk (en) yl or C₁₀-C₃₂A branched alk (en) yl group; and

R₅is-CH₂-or- (C) (CH₃)₂-。

Suitable associative monomers include methacrylates and itaconates having a hydrophilic ethoxylate chain and a hydrophobic alkyl chain.

In one embodiment, the associative monomer is an alkyl ethoxylated methacrylate having the structure of formula I (A):

in one embodiment, the associative monomer is an itaconate-based associative monomer, such as cetyl ethoxylated itaconate, behenyl ethoxylated itaconate, or stearyl ethoxylated itaconate having the structure of formula I (B, C, D, respectively):

in one aspect, the optional associative monomer described under monomer component d), when present, is used in the core polymer or shell copolymer layer in which it is used in an amount in the range of from about 0.01 mol% to about 3 mol%, or in the range of from about 0.05 mol% to about 2 mol%, or in another aspect in the range of from about 0.1 mol% to about 1 mol%, in each case based on the total molar amount of monomers present in the stage excluding the crosslinker.

Crosslinking agent

In one aspect, at least one of the shell copolymer layers of the core-shell polymer includes a crosslinking agent such that the layer containing the crosslinking agent is in a partially or substantially crosslinked network structure. The core may also contain a crosslinking agent, whereby the core will be in a partially or substantially crosslinked network, so long as the mole percentage of crosslinking agent in the core (first stage) polymer is less than the mole percentage of crosslinking agent in the at least one shell (subsequent stage) copolymer layer that includes the crosslinking agent.

The crosslinking agent may be selected from one or more of crosslinking monomers having two or more carbon-carbon double bonds or polyfunctional crosslinking compounds that react with pendant functional groups on the polymer.

Exemplary crosslinking monomers include di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 2 '-bis (4- (acryloyloxy-propoxyphenyl) propane, 2' -bis (4- (acryloyloxydiethoxyphenyl) propane, and zinc acrylate (i.e., 2 (C) 2₃H₃O₂)Zn⁺⁺) (ii) a Tri (meth) acrylate compounds, such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethyl (ethoxylate) propane tri (meth) acrylate and tetramethylolmethane tri (meth)Meth) acrylic acid esters; tetra (meth) acrylate compounds such as ditrimethylolpropane tetra (meth) acrylate, tetramethylolmethane tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate; hexa (meth) acrylate compounds such as dipentaerythritol hexa (meth) acrylate; allyl compounds such as allyl (meth) acrylate, diallyl phthalate, diallyl itaconate, diallyl fumarate and diallyl maleate; polyallyl ethers of sucrose, polyallyl ethers of pentaerythritol, such as pentaerythritol diallyl ether, pentaerythritol triallyl ether and pentaerythritol tetraallyl ether, having 2 to 8 alkyl groups per molecule; polyallyl ethers of trimethylolpropane, such as trimethylolpropane diallyl ether and trimethylolpropane triallyl ether. Other suitable polyunsaturated compounds include divinyl glycol, divinyl benzene and N, N' -methylenebisacrylamide.

In another aspect, suitable polyunsaturated monomers can be synthesized via esterification of a polyol prepared from ethylene oxide or propylene oxide or combinations thereof with an unsaturated anhydride such as maleic anhydride, citraconic anhydride, itaconic anhydride, or addition reaction with an unsaturated isocyanate such as 3-isopropenyl- α - α -xylene isocyanate.

Exemplary polyfunctional crosslinking compounds include polyhaloalkanols, such as 1, 3-dichloroisopropanol and 1, 3-dibromoisopropanol; sulfonium zwitterions, such as tetrahydrothiophene adducts of novolak resins; haloepoxyalkanes such as epichlorohydrin, epibromohydrin, 2-methylepichlorohydrin and epiiodohydrin; polyglycidyl ethers, such as 1, 4-butanediol diglycidyl ether, glycerol-1, 3-diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, bisphenol A-epichlorohydrin epoxy resins, and mixtures of the foregoing. Mixtures of two or more of the foregoing polyfunctional compounds may also be used.

The amount of cross-linking agent in each layer will be selected depending on the desired core-shell polymer characteristics.

In some embodiments where at least one associative monomer is present during at least one core-shell synthesis stage and/or at least one crosslinker is present during the core (first) synthesis stage, when a crosslinker is present, the molar percentage of crosslinker in a given stage is from about 0.01 mol% to about 20 mol% based on the monomers present in the stage excluding the crosslinker, preferably from about 0.03 mol% to about 15 mol% based on the monomers present in the stage excluding the crosslinker, and more preferably from about 0.05 mol% to about 10 mol% based on the monomers present in the stage excluding the crosslinker, and most preferably from about 0.05 mol% to about 7 mol% based on the total moles of monomers present in the stage excluding the crosslinker.

In another embodiment where the associative monomer is not present in any stage of the core-shell particle synthesis, the crosslinking agent is not present during the core (first) stage synthesis, and the mass of the core (first stage) exceeds 60% of the mass of the core-shell particle, the crosslinking agent content of at least one shell (subsequent stage) polymer present during this stage of synthesis can be in the range of about 0.05 mol% to about 20 mol% based on the molar amount of monomer in the shell stage excluding the crosslinking agent, preferably in the range of about 0.05 mol% to 10 mol% based on the molar amount of monomer in the shell stage excluding the crosslinking agent, and most preferably in the range of about 0.1 mol% to about 10 mol% based on the total molar amount of monomer in the shell stage excluding the crosslinking agent.

In yet another embodiment where the associative monomer is not present in any stage of the core-shell particle synthesis, the crosslinking agent is not present during the core (first) stage synthesis, and the mass of the core (first stage) is less than 60% of the mass of the core-shell particle, the crosslinking agent in at least one shell (subsequent stage) polymer during this stage of synthesis may be present in an amount in the range of from about 3 mol% to about 20 mol% based on the molar amount of monomer in the shell stage excluding the crosslinking agent, preferably in the range of from about 3 mol% to 15 mol% based on the molar amount of monomer in the shell stage excluding the crosslinking agent, and most preferably in the range of from about 3 mol% to about 10 mol% based on the molar amount of monomer in the shell stage excluding the crosslinking agent.

Chain transfer agent

Chain transfer agents may be used at any stage of the core-shell polymerization process. The chain transfer agent may be a reducing agent of the disclosureAny chain transfer agent of molecular weight of the segmented polymer of (1). Suitable chain transfer agents include, but are not limited to, compounds containing thio and disulfide groups, such as C₁-C₁₈Alkyl mercaptan, C₁-C₁₈Alkyl mercapto alcohol, mercapto carboxylic acid, mercapto carboxylic ester, thioester, C₁-C₁₈Alkyl disulfides, aryl disulfides, polyfunctional thiols such as trimethylolpropane-tris- (3-mercaptopropionate), pentaerythritol-tetrakis- (thioglycolate) and pentaerythritol-tetrakis- (thioglycolate), dipentaerythritol-hexa- (thioethyl glycolate), and the like; phosphites and hypophosphites; haloalkyl compounds such as carbon tetrachloride, trichlorobromomethane and the like; and catalytic chain transfer agents such as cobalt complexes (e.g., cobalt (II) chelates).

In one aspect, the chain transfer agent is selected from the group consisting of n-dodecyl mercaptan, methyl and 3-mercaptopropionic acid, 2-mercaptoethanol, combinations thereof and the like, octyl mercaptan, tertiary-dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, isooctyl 3-mercaptopropionate, butyl thioglycolate, isooctyl thioglycolate, and dodecyl thioglycolate.

When a chain transfer agent is utilized, it may be present in an amount of less than 0.75 mol% based on the monomers present in the stage excluding the crosslinking agent in one aspect, less than 0.5 mol% based on the monomers present in the stage excluding the crosslinking agent in another aspect, and less than 0.1 mol% based on the monomers present in the stage excluding the crosslinking agent in another aspect.

Core-shell polymer preparation

The core-shell polymers disclosed herein comprise at least two polymers synthesized sequentially via free radical emulsion polymerization techniques known in the art.

The core polymer is synthesized in a first emulsion polymerization step from a monomer composition comprising a) one or more anionic ethylenically unsaturated monomers; b) one or more hydrophobic ethylenically unsaturated monomers; and optionally c) one or more nonionic ethylenically unsaturated monomers, and/or d) one or more associative monomers, and/or e) one or more crosslinkers, all as disclosed above. Chain transfer agents may also be used.

In one embodiment, the core monomer composition is pre-emulsified in a mixture of water and surfactant in the first vessel prior to addition to the reactor for emulsion polymerization, referred to as a monomer pre-emulsion. In another embodiment, the core monomer composition is not added with water or surfactant prior to addition to the reactor where emulsion polymerization occurs, referred to as the monomer mixture.

The core monomer is polymerized in the presence of a suitable free radical forming initiator to provide an emulsion of the core polymer. In one embodiment, the nuclear polymerization reaction preferably begins with a "seeding" procedure in which seed polymer particles are formed, serving as sites for subsequent polymerization reactions.

In the reactor, the monomer composition is introduced into the aqueous feed, optionally containing surfactant, in the form of a monomer pre-emulsion or a separate monomer mixture and an aqueous surfactant solution. When a monomer mixture is used, the aqueous surfactant solution may be added to the reactor at the same time as the monomer mixture is added or immediately after the monomer mixture is added. The reactor contents were stirred and a small amount of free radical initiator was added to the reactor to initiate the formation of seed particles.

After completion of the seeding stage, the monomer composition required to complete the core may be added in the form of a monomer pre-emulsion simultaneously with the initiator feed, or in the form of a monomer mixture simultaneously with the aqueous surfactant solution feed and the initiator feed. Alternatively, the initiator may be added prior to adding the monomer composition to the reactor.

Next, a shell polymer is formed in a second polymerization step. The monomer composition required to form the shell may be added simultaneously with the initiator feed in the form of a monomer pre-emulsion or in the form of a monomer mixture with the aqueous surfactant solution feed and the initiator feed. Alternatively, the initiator may be added prior to adding the monomer composition to the reactor. The final product is a two-stage polymer comprising a core surrounded or partially surrounded by a shell, wherein the mole percentage of the crosslinking agent in the core is lower than the mole percentage of the crosslinking agent in the shell.

In an alternative embodiment of the process for preparing the core-shell polymer, initially only a portion of the complete amount of surfactant is present in the reactor and the remainder is added during all steps of the polymerization as a co-existing stream along with the monomer composition stream and the initiator stream.

Optionally, a further continuous free radical emulsion polymerization stage may be conducted to obtain a multi-layer polymer morphology such that the continuous polymer stage differs at least by the mole percentage of crosslinker present in that stage, provided that the core or first stage polymer must have a mole percentage of crosslinker that is lower than that of the at least one shell polymer layer. In stages where it is desired to have a linear polymer, the emulsion polymerizable monomer composition will be absent a crosslinking agent, and in stages where it is desired to have a crosslinked polymer, the emulsion polymerizable monomer composition will include a crosslinking agent.

To achieve the desired properties for any particular end use application, in preparing the core-shell polymers as disclosed herein, any of the following can be adjusted: (i) the relative molar ratios of the individual monomers, (ii) the respective mass percentages of the core and shell stages in the core-shell polymer, (iii) the choice of monomer, crosslinker or associative monomer in any layer, (iv) the rates of addition of the monomer mixture, surfactant solution and initiator solution, and (v) the molar percentage of crosslinker in any layer, provided that the molar percentage of crosslinker in the core (first stage) is less than the molar percentage of crosslinker in at least one of the shell (subsequent stage) layers.

Although the core-shell polymer is synthesized by successive emulsion polymerization steps to give the aqueous polymer emulsion, it will be appreciated that the core-shell polymer may be supplied in dry powder form, if desired.

The emulsion polymerization may be conducted in a staged batch process, a staged semi-batch monomer addition process, or a multi-step continuous process, or the polymerization reaction may be initiated in a batch process and then the majority of the monomer may be continuously added to the reactor in stages (seeded semi-batch process), as discussed above.

Typically, the emulsion polymerization is conducted at a reaction temperature in the range of from about 20 to about 99 ℃, although higher or lower temperatures may also be used.

The emulsion polymerization can be carried out in an aqueous or aqueous-alcoholic medium.

The surfactant may be added to the monomer composition to form a pre-emulsion, or the surfactant may be added directly to the polymerization reactor during emulsion polymerization, or both. In one embodiment, the emulsion polymerization is carried out in the presence of a surfactant in an amount ranging from about 0.01% to about 10% by weight in one aspect, from about 0.1% to about 5% by weight in another aspect, and from about 0.3% to about 3% by weight in another aspect, based on the total emulsion weight.

Suitable surfactants include anionic, nonionic, amphoteric and cationic surfactants, and mixtures thereof. Most commonly, anionic and nonionic surfactants can also be used in the form of mixtures thereof.

Suitable anionic surfactants for facilitating emulsion polymerization are well known in the art and include, but are not limited to, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, (C)₆-C₁₆) Sodium alkyl phenoxy benzene sulfonate, (C)₆-C₁₆) Disodium alkyl phenoxy benzene sulfonate, (C)₆-C₁₆) Disodium dialkylphenoxybenzene sulfonate, disodium laureth-3 sulfosuccinate, sodium dioctyl sulfosuccinate, sodium di-sec-butylnaphthalene sulfonate, disodium dodecyl diphenyl ether sulfonate, disodium n-octadecyl sulfosuccinate, phosphate esters of branched alcohol ethoxylates, and the like.

Nonionic surfactants suitable for facilitating emulsion polymerization are well known in the polymer art and include, but are not limited to, linear or branched alcohol ethoxylates, C₈To C₁₂Alkylphenol alkoxylates such as octylphenol ethoxylates, polyoxyethylene polyoxypropylene block copolymers, and the like. Other useful nonionic surfactants include C₈To C₂₂Polyoxyethylene glycol fatty acid ester, monoglyceride and diglyceride, and dehydrationSorbitol ester and ethoxylated sorbitan ester, C₈To C₂₂Fatty acid glycol esters, block copolymers of ethylene oxide and propylene oxide having an H L B value greater than about 12, ethoxylated octylphenols, and combinations thereofC-17、A-38 anda-39 Polyglycolether of cetearyl alcohol (a mixture of cetyl alcohol and stearyl alcohol). In yet another embodiment, the polyoxyethylene polyoxypropylene block copolymer comprises the BASF corporation under the trade nameF127 andl35, respectively.

Other suitable nonionic surfactants include, but are not limited to, ethoxylated linear fatty alcohols, such asA5060 (Cognis), Ethal L A-23 and Ethal L A-50(Ethox Chemicals); branched alkyl ethoxylates, e.g.X 1005(Clariant Corp.)、C₁₂To C₁₄Secondary alcohol ethoxylates, e.g.S15-30 and S15-40(Dow Chemical Co.); surfactants based on ethoxylated octylphenols, e.g.X-305, X-405 and X-705(Dow Chemical Co.)CA 407, 887 and 897(Rhodia, Inc.),OP 3070 and 4070(BASF Corp.),OP 30 and 40 (Uniqema); block copolymers of ethylene oxide and propylene oxide, e.g.L35 and F127(BASFCorp.), and C₁₁Secondary alcohol ethoxylates, e.g.EPN407(Clariant Corp.). A number of other suppliers are found in the commercial literature.

In addition, suitable Surfactants are also described in The Handbook of industrial Surfactants (fifth edition, Michael and Irene Ash), which is hereby incorporated by reference in its entirety.

The emulsion polymerization may be carried out in the presence of a suitable polymer stabilizer. Suitable polymeric stabilizers (also known as protective colloids) for use in the emulsion polymerization process of the present invention are water-soluble polymers including, for example, synthetic polymers such as polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide, carboxylate-functional addition polymers, polyalkyl vinyl ethers, and the like; water-soluble natural polymers such as gelatin, pectin, alginate, casein, starch and the like; and modified natural polymers such as methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, allyl-modified hydroxyethylcellulose, and the like. In some cases it is advantageous to use mixtures of synthetic and natural protective colloids, for example mixtures of polyvinyl alcohol and casein. Other suitable natural polymers are mixed ethers, such as methylhydroxyethyl cellulose and carboxymethyl methyl cellulose. The polymeric stabilizer may be used in an amount up to about 10 wt%, based on the total emulsion weight, or up to about 7.5 wt%, or up to about 5 wt%, or up to about 2.5 wt%, or up to about 2 wt%, based on the total emulsion weight. In another embodiment, when a polymeric stabilizer is utilized, the amount of polymeric stabilizer included ranges from about 0.001 wt% to about 10 wt%, or from about 0.01 wt% to about 7.5 wt%, or from about 0.1 wt% to about 5 wt%, or from about 0.5 wt% to about 2.5 wt%, or even from about 1 wt% to about 2 wt%, based on the total emulsion weight.

In free radical emulsion polymerization, free radical initiators are utilized which generate free radicals during the polymerization process. As used herein, an initiating system is any free radical initiating system. The free radical initiator is present in an amount ranging from about 0.01 wt% to about 3 wt% based on the total monomer weight. In one embodiment, the initiating system is soluble in water to at least 0.1% by weight at 25 ℃. Suitable initiators include, but are not limited to, peroxides, azo initiators, and redox systems, such as hydrogen peroxide and erythorbic acid, and metal ion-based initiation systems. Initiators may also include inorganic and organic peroxides such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide and lauryl peroxide; organic hydroperoxides such as cumene hydroperoxide and tert-butyl hydroperoxide. In one embodiment, inorganic peroxides such as sodium persulfate, potassium persulfate, and ammonium persulfate are preferred. In another embodiment, the initiator comprises a metal ion-based initiation system comprising Fe and hydrogen peroxide, and Fe in combination with other peroxides. Organic peroxyacids, such as peroxyacetic acid, may be used. The peroxides and peroxyacids may optionally be activated with reducing agents such as sodium bisulfite, sodium formaldehyde or ascorbic acid, transition metals, hydrazine, and the like. Azo initiators, especially water-soluble azo initiators, may also be used. Water-soluble azo initiators include, but are not limited to, 2 '-azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride, 2' -azobis [2- (2-imidazolin-2-yl) propane ] disulfate dihydrate, 2 '-azobis (2-methylpropionamidine) dihydrochloride, 2' -azobis [ N- (2-carboxyethyl) -2-methylpropionamidine ] hydrate, 2 '-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl ] propane } dihydrochloride, 2' -azobis [2- (2-imidazolin-2-yl) propane ]), 2,2' -azobis (1-imino-1- (N-pyrrolidinyl) -2-ethylpropane) dihydrochloride, 2' -azobis { 2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyethyl ] propionamide }, 2' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], and the like. Oil-soluble free radical generators, such as 2,2' -azobisisobutyronitrile and the like, and mixtures thereof, may also be used.

Optionally, other emulsion polymerization additives and processing aids well known in the art of emulsion polymerization may be included in the polymerization system, such as co-emulsifiers, solvents, buffers, chelating agents, inorganic electrolytes, polymer stabilizers, biocides, defoamers, and pH adjusters.

In one aspect, one may select from ethoxylated C' s₁₀To C₂₂A co-emulsification aid of a fatty alcohol (or mixture thereof) is added to the polymerization medium. In one aspect, the fatty alcohol contains from about 5 to about 250 moles of ethoxylation, in another aspect from about 8 to 100 moles, and in another aspect from about 10 to 50 moles. Exemplary ethoxylated fatty alcohols include lauryl alcohol ethoxylate, myristyl alcohol ethoxylate, cetyl alcohol ethoxylate, stearyl alcohol ethoxylate, cetearyl alcohol ethoxylate, sterol ethoxylate, oleyl alcohol ethoxylate, and behenyl alcohol ethoxylate. In another aspect, suitable ethoxylated fatty alcohols include ceteth-20, ceteareth-20 and steareth-20, behenyl ether-25 and mixtures thereof.

If ethoxylated fatty alcohols are employed, the amount of ethoxylated fatty alcohols may range from about 0.01% to 10% by weight in one aspect, from about 0.1% to about 5% by weight in another aspect, and from about 0.3% to about 3% by weight in another aspect, based on the total weight of the emulsion.

A typical two-stage polymerization is described below. First, a core-stage monomer composition comprising a) one or more anionic ethylenically unsaturated monomers is added to a first vessel and to a solution of an emulsifying surfactant (e.g., an anionic surfactant) in water to prepare a monomer pre-emulsion, with mixing; b) one or more hydrophobic ethylenically unsaturated monomers; and optionally c) one or more non-ionic ethylenically unsaturated monomers, and/or d) one or more associative monomers, and/or e) one or more cross-linking agents, and/or chain transfer agents (all as disclosed above). Optional processing aids (e.g., co-emulsifiers) can be added if desired.

The polymerization reactor is charged with the required amount of water, additional surfactant and optional processing aid. The polymerization reactor was equipped with an attached inert gas inlet and feed pump, and the reactor contents were maintained under an inert atmosphere and heated with mixing agitation. The reactor contents were brought to a temperature in the range of about 55 to 98 c and maintained at that condition for about one hour. The inoculation stage is carried out by means of a pre-emulsion as described above, in a manner consistent with the addition of monomers and surfactants. The desired amount of the core stage monomer pre-emulsion is fed subsurface into the reactor and the free radical initiator solution is fed into the reactor contents separately and simultaneously from the core stage monomer composition over a period of about half an hour to two hours. During this time, the reaction temperature was controlled in the range of about 45 to about 95 ℃.

After the desired amount of the core monomer composition is added to the reactor, the feed can be stopped and, if desired, an additional amount of free radical initiator can optionally be added to the reactor. The resulting reaction mixture may be maintained at a temperature of about 45 to 95 ℃ for a period of time sufficient to complete or substantially complete the polymerization reaction and obtain the first stage core polymer particle emulsion.

The shell stage monomer composition containing the required supplemental amounts of shell stage monomer and other components listed above with respect to the core stage monomer composition, including the crosslinker, can be mixed in a separate container following the same procedure outlined with respect to formulating the core stage monomer composition.

Alternatively, the crosslinking agent can be added to a first vessel containing the remaining materials of the core-stage monomer composition and mixed under agitation to form the shell-stage or second-stage monomer composition. Additional shell stage monomers can be added to the composition if desired.

The shell stage or second stage monomers are metered into the polymerization reactor at a constant rate and mixed with the core polymer emulsion. While feeding the shell stage monomer, an amount of free radical initiator solution sufficient to reinitiate the polymerization reaction is metered into the reaction mixture such that the shell stage or second stage monomer is polymerized in the presence of the core stage or first stage polymer. The temperature is then maintained at about 85 ℃ for about half an hour to two and a half hours or until the polymerization reaction is complete. Unreacted monomer can be removed by performing monomer addition steps, such as adding additional initiator or by adjusting the temperature and maintaining for a period of time to maintain free radical flow from the thermal initiator residue, as is well known in the art of emulsion polymerization. Typically, the segmented core-shell polymer or segmented polymer emulsion product has a total polymer solids content in the range of about 10 to about 45 weight percent. Although the polymer is synthesized in emulsion form, it is recognized that the segmented core-shell polymer can be supplied in dry powder form, if desired.

Although a typical two-stage polymerization process has been generally described above, a multi-stage or multi-layer polymer may be formed via sequential emulsion polymerization of monomer feeds in the presence of polymer particles of a previously formed emulsion polymer.

Dry rheology modifier compositions

In one aspect, the rheology modifier composition can be in the form of a dry rheology modifier. In one embodiment, the rheology modifier composition may be dried by spray drying.

The invention further relates to a process for preparing a rheology modifier composition comprising co-mixing a core-shell polymer with a spray drying aid and drying the resulting mixture.

In one aspect, the presence of a spray drying aid may facilitate spray drying. In some embodiments, the spray drying aid is derived from a natural renewable resource. The natural renewable resource may be a polysaccharide, such as starch or cellulose. Alternatively, the spray drying aid may be a derivative of polyvinyl acetate. In some embodiments, the spray drying aid is present in the emulsion polymer composition during the polymerization process. In some embodiments, the spray drying aid is blended into the emulsion polymerization product prior to spray drying.

The core-shell polymer that is emulsion polymerized as described above and then co-mixed with the spray drying aid polymer may be dried, preferably by spray drying, to provide a dried rheology modifier composition in the form of a stable powder. The spray drying aid may be a polysaccharide, suitable examples of which include starch and cellulose, and derivatives thereof. Other suitable spray drying aids include polyvinyl acetate derivatives such as polyvinyl alcohol, polyvinyl alcohol/polyvinyl acetate copolymers, and other polyvinyl alcohol copolymers. Spray drying aids may be used to impart additional desirable texture and rheological properties to the formulations in which the dried rheology modifiers of the present application may be used.

As used herein, the term "dry rheology modifier composition" means a composition comprising at least one core-shell polymer and at least one polysaccharide in an anhydrous form comprising less than 25 wt% water, in one embodiment less than 20 wt% water, in one embodiment less than 10 wt% water, in one embodiment less than 5 wt% water, in one embodiment less than 2 wt% water, in one embodiment less than 1 wt% water, in one embodiment less than 0.5 wt% water.

The polysaccharide component enables the resulting composition to be dried to produce a dried rheology modifier composition containing less than 25% by weight water. Without being bound by theory, it is believed that the higher glass transition temperature of the polysaccharide polymer makes it easier to dry the rheology modifier composition. In one embodiment, the glass transition temperature of the polysaccharide polymer is at least 50 ℃, in one embodiment at least 75 ℃, and in one embodiment at least 90 ℃.

The weight percentage of the polysaccharide polymer or other spray drying aid is at least about 20 wt% of the dried rheology modifier composition, preferably at least about 25 wt% of the dried rheology modifier composition, and most preferably at least about 30 wt% of the dried rheology modifier composition. The maximum weight percentage of the polysaccharide polymer or other spray drying aid is no more than about 90 wt% of the dried rheology modifier composition, in another embodiment preferably no more than about 85 wt% of the dried rheology modifier composition, and in yet another embodiment most preferably no more than about 80 wt% of the dried rheology modifier composition.

In yet another embodiment, the dried rheology modifier composition comprises a mixture of the products of at least two different core-shell copolymer compositions.

In yet another embodiment, the dried rheology modifier composition comprises more than one polysaccharide polymer or other spray drying aid.

Optionally, prior to the drying step, a second composition is added, the second composition comprising a second core-shell polymer and optionally a second polysaccharide polymer or other spray drying aid, wherein the second core-shell polymer and optionally the second polysaccharide polymer or other spray drying aid in the second composition may each be the same as or different from the at least one core-shell polymer and the at least one polysaccharide polymer, respectively, in the initial polymer blend.

The particle size of the solid product can be adjusted using methods known in the art, such as milling.

Spray drying aid polymers

In one aspect, a rheology modifier as disclosed herein can be co-mixed with a spray drying aid polymer prior to spray drying. Suitable spray drying aid polymers include polysaccharide polymers including, but not limited to, starch and starch derivatives, cellulose and cellulose derivatives, and gums; and polyvinyl acetate derivatives.

Polysaccharide polymers

Polysaccharides useful as spray drying aid polymers may be derived from plant, animal, and microbial sources. Examples of such polysaccharides include starch, cellulose, gums (e.g., acacia, guar and xanthan), alginates, pectin, carrageenan, inulin and gellan, and derivatives of each of the foregoing. One skilled in the art will recognize that polysaccharides may need to be depolymerized or derivatized to be water soluble. For example, it may be desirable for the starch to depolymerize to 1 million or less molecular weight in order to be water soluble. Similarly, derivatization of cellulose, for example to carboxymethyl cellulose, may be required to provide water solubility.

The weight average molecular weight of the polysaccharide based spray drying aid polymer may be about 20,000,000 or less, or 10,000,000 or less, or about 1,000,000 or less, or about 100,000 or less, or about 10,000 or less.

Starch and starch derivatives

Starches include starches derived from corn and known corn hybrids such as waxy corn and high amylose (greater than 40% amylose) corn, as well as other starches such as potato, tapioca, wheat, rice, pea, sago, oat, barley, rye, and amaranth, including known hybrids or genetically engineered materials. The starch may belong to a natural variety or a hybrid variety produced by traditional breeding schemes or by artificial genetic manipulation. These hybrids include, but are not limited to, waxy forms (starches with little or no amylose) and high amylose cultivars. Waxy starches are generally defined as having about 5% or less amylose and sometimes containing about 2% or less amylose. In one embodiment, the waxy starch has a percentage of amylopectin of about 95% or greater. High amylose starch is defined as having about 40% or greater percent amylose (with the exception of pea starch having a high amylose content of about 27% or greater percent amylose). In another embodiment, the high amylose starch has an amylose content of about 60% or greater percent amylose. Also included in the present application are starches having altered chain length and branch points.

In one embodiment, preferred polysaccharides are starches and starch derivatives, including but not limited to thermally and/or mechanically treated starches; oxidized, hydrolyzed, or enzymatically degraded starches; and chemically modified starches. These preferred polysaccharides include maltodextrins, dextrins, pyrodextrins, oxidized starches, cyclodextrins, and substituted cyclodextrins, as well as higher molecular weight starches, or derivatives thereof. In another preferred embodiment, the preferred starches are waxy maltodextrins, waxy dextrins, waxy pyrodextrins, waxy oxidized starches and waxy starches of higher molecular weight, or derivatives thereof. The most preferred starch is waxy maltodextrin. Chemical modifications include hydrolysis, esterification or etherification under the action of acids, enzymes, oxidizing agents or heat. After the chemical modification, the chemically modified starch may be cationically, anionically, non-ionically or amphoteric or hydrophobically modified.

In one embodiment, the polysaccharide is maltodextrin, a polymer having d-glucose units linked primarily through α -1,4 linkages and a dextrose equivalent ('DE') of about 20 or less.

Suitable polysaccharides may further include corn syrup. Corn syrup is defined as a degraded starch product with a DE of 27 to 95. Examples of specialty corn syrups include high fructose corn syrup and high maltose corn syrup. Although not strictly limited to polymers, monosaccharides and oligosaccharides, such as galactose, mannose, sucrose, maltose, fructose, ribose, trehalose, lactose, and the like may also be used as spray drying aids in the disclosed compositions and methods, and for purposes herein are considered to be within the scope of spray drying aid polymers.

In one embodiment, the DE of the polysaccharide is about 65 or less, 45 or less, 20 or less, in another embodiment about 15 or less, and in yet another embodiment about 5 or less. In one embodiment, the DE of the polysaccharide is within a range having a lower limit of at least about 1.

For purposes of this application, pregelatinized Starch is also known as cold water soluble Starch (CWS) and the terms are used interchangeably.A review on how to prepare pregelatinized Starch is described (Starch; Chemistry and Technology, R. L. Whistler, second edition, Academic Press, Inc. New York,1984, page 670 @, 673.) furthermore, these products may be prepared by co-jet cooking coupled to a spray dryer (see Kasica et al, U.S. Pat. No. 5,571,552.) the pregelatinized Starch may be prepared by different methods including, but not limited to, drum drying, spray cooking or spray cooking, in addition to precooking, which is suitable for use in the preparation of modified anionic Starch, which may also be described in modified Starch containing anionic Starch derivatives, as well as modified Starch derivatives in Boiff Starch-soluble form in the Boiff reaction, and subsequent gelling reaction in a modified Starch-soluble in a modified Starch-type, which may be described in the book by means of modification, including, spray cooking or extrusion, and which may be subsequently modified by a reaction in modified anionic Starch modified Starch-modified Starch type-Boifferen-modified Starch-1984-and modified Starch soluble in Starch soluble form-Water.

Cellulose and cellulose derivatives

In one embodiment, the polysaccharide is cellulose and/or derivatives thereof, such as carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), carboxymethyl hydroxyethyl cellulose (CMHEC), hydroxypropyl cellulose, sulfoethyl cellulose and derivatives thereof, ethyl hydroxyethyl cellulose (EHEC), methyl ethyl hydroxyethyl cellulose (MEHEC), and hydrophobically modified ethyl hydroxyethyl cellulose HM-EHEC, some of which are available from akzo nobel. Polysaccharides also include cellulose derivatives, including plant heteropolysaccharides, commonly referred to as hemicelluloses, which are by-products of the pulp and paper industry. Hemicelluloses include xylan, glucuronoxylan, arabinoxylan, glucomannan and xyloglucan. Xylan is the most common heteropolysaccharide and is preferred. Polysaccharides, such as degradation products of cellulose, such as cellobiose, are suitable for preparing polymers as disclosed herein. Polysaccharides also include inulin oligosaccharides and derivatives thereof, such as carboxymethylinulin oligosaccharides. In one embodiment, preferred cellulosic materials are carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), carboxymethyl hydroxyethyl cellulose (CMHEC), hydroxypropyl cellulose, ethyl hydroxyethyl cellulose (EHEC), methyl ethyl hydroxyethyl cellulose (MEHEC), and hydrophobically modified ethyl hydroxyethyl cellulose (HM-EHEC).

Gum (a kind of food)

Suitable polysaccharides include guar gum, unwashed guar gum, washed guar gum, cationic guar gum, carboxymethyl guar gum (CM guar), hydroxyethyl guar gum (HE guar), hydroxypropyl guar gum (HP guar), carboxymethyl hydroxypropyl guar (CMHP guar), hydrophobically modified guar gum (HM guar), hydrophobically modified carboxymethyl guar (HMCM guar), hydrophobically modified hydroxyethyl guar (HMHE guar), hydrophobically modified hydroxypropyl guar (HMHP guar), cationic hydrophobically modified hydroxypropyl guar (cationic HMHP guar), hydrophobically modified carboxymethyl hydroxypropyl guar (HMCMHP guar), hydrophobically modified cationic guar (cationic guar), cationic guar (cationic HM guar), cationic guar (cationic guar), and mixtures thereof, Guar gum hydroxypropyl triammonium chloride, hydroxypropyl guar gum hydroxypropyl triammonium chloride.

Polyvinyl acetate derivatives

Suitable polyvinyl acetates and derivatives thereof include polyvinyl alcohol, polyvinyl alcohol/polyvinyl acetate copolymers and vinyl acetate copolymers, and polyvinyl alcohol/polyvinyl acetate graft copolymers, and polyvinylpyrrolidone. The derivative of polyvinyl acetate may be anionic, such as a copolymer with an anionic ethylenically unsaturated monomer, or nonionic, such as a copolymer with a nonionic ethylenically unsaturated monomer.

The polyvinyl acetate derivative can be a completely or partially saponified and/or modified polyvinyl alcohol, the degree of hydrolysis of which is preferably from about 70 to 100 mol%, in particular from about 80 to 98 mol%, and the Hoppler viscosity (Hoppler viscocity) in a 4% aqueous solution is preferably from 1 to 50mPas, in particular from about 3 to 40mPas (measured at 20 ℃ according to DIN 53015). If the polyvinyl acetate-based polymer is reacted to form a dry emulsion rheology modifier, the weight average molecular weight may be about 1,000,000 or less, or 500,000 or less, or about 100,000 or less. The polyvinyl acetate-based polymer may have a weight average molecular weight of about 100,000 or less, or about 50,000 or less, or about 10,000 or less.

In one embodiment of the invention, the protective water-soluble polymer is selected from polyvinylpyrrolidone and derivatives. Preferably, the polyvinylpyrrolidone is a homopolymer, but copolymers may also be used. When polyvinylpyrrolidone is used, the polymer may have any molecular weight as long as the rheology modifier remains effective. For example, when polyvinylpyrrolidone is used, it may specifically be PVP K-15 (average molecular weight 10,000), K-30 (average molecular weight 40,000) or K-90 (average molecular weight 360,000) manufactured by Ashland.

The weight average molecular weight of the spray drying aid polymer as starch can be determined by the following procedure:

a2.00 mg/ml starch sample was prepared in a solution of 0.03M NaCl in Dimethylformamide (DMSO). the starch sample solution was heated at 100 ℃ for 60 minutes and clarified after heating.the solution was filtered using a 0.45 micron filter.

Column Phenogel L inear 230 cm × 7.8.8 mm

The temperature is 60 DEG C

DMSO solution of 0.03M NaCl as solvent

Flow rate 0.60ml/min

Detection of Wyatt Heleos 18 Angle MA L S and Optilab Rex refractive indices

The dry rheology modifier compositions disclosed herein can comprise an anti-caking agent. Examples of anti-caking agents include, but are not limited to, kaolin, aluminosilicates, silica, aluminum silicon oxides, calcium carbonate, magnesium sulfate, talc, gypsum, silica and silicates, and mixtures thereof. The particle size of the anticaking agent is preferably in the range of 100nm to 10 μm. More than one anti-caking agent may be used.

When the core-shell rheology modifier of the invention is dried in the presence of the spray drying aid polymer, the core-shell polymer is first prepared as described above and then the spray drying aid polymer is added. The core-shell polymer composition may be diluted prior to addition of the spray drying aid polymer. In one embodiment, the aqueous composition with the spray drying aid polymer is added to the core-shell polymer composition in a suitably mixed amount. Alternatively, the core-shell polymer composition may be added to an aqueous composition having a spray drying aid polymer. In one embodiment, the dried spray drying aid polymer is added to the core-shell polymer composition while diluting in water. The weight percentage of the core-shell in the core-shell composition may be in the range of 5-50% and preferably in the range of 10-30%. The solids in the aqueous composition with the spray drying aid polymer may be in the range of 5-50% and preferably in the range of 10-30%. The solids in the aqueous blend of core-shell polymer and spray drying aid polymer may be in the range of 5 to 50% and preferably in the range of 10 to 30% and most preferably in the range of 15 to 25%. This blend may be dried as such or, if desired, may be further diluted prior to drying. The preferred drying method is spray drying. However, other methods such as drum drying, tray drying, fluidized bed drying, etc. may also be used. The spray drying aid polymers described herein will be suitable for use in any of these alternative drying methods.

Product formulations

In the following description of product formulations that may be prepared with the rheology modifiers disclosed herein, unless otherwise stated, the term "rheology modifier" is intended to include core-shell polymers that are in liquid form or dried to solid form in the presence or absence of the co-mixed spray drying aid polymer.

Product formulations comprising the rheology modifier composition as disclosed herein may be selected from personal care products, home care products, healthcare products, institutional and industrial care products, adhesives, coatings, formulations in agriculture and for the electronics component industry, and formulations for the construction industry, among other applications. The present application further relates to the use of the rheology modifier composition as disclosed herein as a component of such product formulations as well as the product formulation active ingredients.

As used herein, "home care products" include, but are not limited to, products used in household residences for surface cleaning or maintaining hygiene, such as in kitchens and bathrooms (e.g., hard surface cleaners, furniture polishes, manual and automatic dishwashing formulations, toilet bowl cleaners and disinfectants), and laundry products used for fabric care and cleaning (e.g., cleaners, fabric conditioners, pre-treatment stain removers), and the like.

As used herein, the term "healthcare product" includes, but is not limited to, pharmaceuticals (controlled release pharmaceuticals); cosmeceutical products; oral care (oral and dental) products such as oral suspensions, mouthwashes, toothpastes, tooth powders and the like; and over-the-counter products and devices (topical and transdermal) for external application to the body, including the skin, scalp, nails and mucous membranes of humans and animals, such as patches, plasters and the like, for improving health-related conditions or medical conditions, for daily maintenance of hygiene or health, and similar applications.

As used herein, the term "institutional and industrial care" ("I & I") includes, but is not limited to, products used for surface cleaning or maintaining hygiene in institutional and industrial environments, textile treatments (e.g., textile conditioners, carpet and matting cleaners), automotive care (e.g., manual and automatic car wash cleaners, tire brighteners, leather conditioners, liquid car polishes, plastic polishes and conditioners), paints and coatings, and the like.

In agricultural applications, the disclosed rheology modifier compositions may be used in agrochemical formulations. Which may impart stabilizing, thickening, dispersing or suspending properties to the agrochemical formulation due to its rheological properties. One particularly useful agrochemical formulation is Suspension Concentrate (SC). Another particularly useful agrochemical formulation is a solid formulation comprising a Wettable Powder (WP), Water Dispersible Granules (WDG) and Water Soluble Granules (WSG). When an agrochemical formulation comprising the disclosed rheology modifier composition is diluted in water, the disclosed rheology modifier composition can stabilize the agrochemical or suspend it in a diluted aqueous system.

In oilfield applications, the disclosed rheology modifier compositions may be used in formulations used in fracturing operations. In some applications, it is desirable to use a liquid composition having viscoelastic properties. Such compositions are useful, for example, to stimulate oil wells where a hindered flow path results in insufficient production of hydrocarbons, a technique known as (hydraulic) fracturing and a specialized fluid used in the technique known as a fracturing fluid. For such fracturing methods, the composition is typically injected into the formation through the wellbore at sufficient pressure to create fractures in the formation rock, thereby creating channels through which hydrocarbons can more easily flow into the wellbore. In one embodiment, the fracturing fluid should create a minimal pressure drop in the tubing within the wellbore during placement and have a suitable viscosity to carry the proppant (sand) material that prevents this fracture closure. In addition, the fracturing fluid should have a minimal leak-off rate to avoid migration of the fluid into the formation rock, whereby fractures can be significantly created and propagated, and should degrade to avoid leaving residual material that may prevent accurate flow of hydrocarbons into the wellbore.

Other formulations in which the disclosed rheology modifiers can be used include adhesives, asphalt emulsions, paints and coatings, superabsorbents and other industrial applications.

In one embodiment, the rheology modifier composition added to the formulations may be at least about 0.1% modifier by weight of the formulation, more preferably at least about 0.5% modifier by weight of the formulation and most preferably at least about 1.0% modifier by weight of the formulation. The rheology modifier composition added to the formulations may be up to about 20% modifier by weight of the formulation, more preferably up to about 15% modifier by weight of the formulation and most preferably up to about 10% modifier by weight of the formulation.

Rheology modifiers can be used in aqueous protective coating compositions. The desired level of these rheology modifiers increases and maintains viscosity under specific processing conditions and end use conditions. In particular, the rheology modifiers can be used in all types of coatings, such as decorative and protective coatings. Rheology modifiers can be used as rheology modifiers in water-based protective coating compositions. Water-based protective coating compositions are commonly referred to as latex paints or dispersion paints and have been in existence for many years. Adjusting the rheology of such aqueous protective coating compositions is challenging because the coating composition must provide good leveling and good sag resistance, yet its viscosity should not be too low or too high to be easily applied.

The polymers disclosed herein may be used in paper coating applications. Paper coating formulations impart certain qualities to the paper, including weight, surface gloss, smoothness, or lower ink absorption. The uniform coating on the paper promotes enhanced print surface and properties such as coverage, smoothness and gloss can be improved. Paper and paperboard grades are sometimes coated to improve the printability, visual properties, or functionality of the sheet. The properties and printability of coated paper are affected by the substrate sheet (fiber type, sheet formation, internal sizing and substrate weight), coating materials (pigment type, binder type, rheology modifiers, water retention aids, lubricants, defoamers, etc.), coating formulation (ratio of coating components, solids and pH), coating method (coating application type and speed), coating weight, drying conditions (dryer type, drying temperature, drying time and final moisture content), etc.

Paper coating formulations typically contain three main classes of ingredients: pigment, binder and additive. The pigment improves the printing and optical properties of the sheet, the binder adheres the pigment particles to each other and to the sheet, and the additive aids in the coating process or enhances the sheet properties. An important additive used in paper coating formulations is a rheology modifier. Rheology modifiers are used to achieve desired rheological properties and improved flow during the coating process.

The rheology modifier compositions disclosed herein unfold when neutralized in a coating formulation, thereby increasing the viscosity. This viscosity increase helps control the pick-up rate on the applicator roll, affects the flow characteristics during the metering procedure and changes the fixing and leveling characteristics after the metering step in the coating process. The ratio of hydrophilic to hydrophobic monomers in the polymer affects the water retention characteristics and the degree of interaction with the binder. The molecular weight of the polymer and its branching affect the low shear viscosity and high shear viscosity profile.

Rheology modifier compositions containing hydrophobically modified alkali swellable polymers are also useful in paper coating applications such products are very effective in light weight coatings (L WC) these products are used in high solids carbonate coatings that require water retention and produce minimal high shear viscosity.

As used herein, the term "personal care product" includes, but is not limited to, cosmetics, toiletries, pharmaceuticals, skin care aids, insect repellents, personal hygiene and cleansing products that are applied to the body, including the skin, hair, scalp and nails of humans and animals. Personal care applications include, but are not limited to, formulations for hair styling gels, skin creams, tanning lotions, sunscreens, moisturizers, toothpaste, medical and first aid ointments, cosmetic ointments, suppositories, cleansers, lip gloss, mascara, hair dyes, pomades, shampoos, body soaps and deodorants, hair care and styling formulations, shaving preparations, depilatories and hand washes, including alcohol-based hand washes.

Suitable personal care applications also include formulations for use on the skin, eyelashes, or eyebrows, including (but not limited to) cosmetic compositions such as mascaras, facial foundations, eyeliners, lipsticks, and color cosmetic products; skin care compositions such as moisturizing lotions and creams, skin treatment products, skin protection products in the form of emulsions, liquids, sticks or gels; sunscreen care products such as sunscreens, sunscreen lotions, creams, sunscreen emulsion sprays, liquid/alcohol sunscreen sprays, sunscreen water gels, broad spectrum sunscreens containing UVA and UVB actives, sunscreens containing organic and inorganic actives, sunscreens containing combinations of organic and inorganic actives, tanning products, self-tanning products, after-sun products, and the like. Particularly suitable compositions are personal care emulsions, more particularly, sunscreen care compositions such as sunscreen emulsions and sunscreen emulsion sprays are suitable. The personal care composition may be in any form including, but not limited to, sprays, emulsions, lotions, gels, liquids, sticks, waxes, pastes, powders, and creams.

The personal care composition may also include other optional components commonly used in the industry, and these components will vary greatly depending on the type of composition and the functionality and characteristics desired. These components include, but are not limited to, thickeners, suspending agents, emulsifiers, UV filters, sunscreen actives, moisturizers, emollients, oils, waxes, solvents, chelating agents, vitamins, antioxidants, botanical extracts, silicones, neutralizers, preservatives, fragrances, dyes, pigments, conditioners, polymers, antiperspirant actives, anti-acne agents, anti-dandruff actives, surfactants, exfoliants, depilatory actives, film formers, propellants, tanning accelerators, hair fixatives, and colorants. The polymer is compatible with most other components used in known personal care compositions. For example, the sunscreen composition may contain at least one component selected from the group comprising: organic UV filters, inorganic UV actives, UVA and/or UVB sunscreen actives, oxiranyl esters (octinoxate), oxiranyl esters (octisalate), oxybenzone (oxybenzone), homosalate (homosalate), octocrylene (octocrylene), avobenzone (avobenzone), titanium dioxide, starch, modifiers, emulsifiers, other rheology modifiers and thickeners, neutralizers, emollients, solvents, film formers, moisturizers, antioxidants, vitamins, chelating agents, preservatives, fragrances, and zinc oxide. The skin care and cosmetic composition may contain at least one component selected from: vitamins, anti-aging agents, moisturizers, emollients, emulsifiers, surfactants, preservatives, pigments, dyes, colorants, and insect repellents.

In a personal care formulation as defined herein, various other additives, such as active and functional ingredients, including, but not limited to, emollients, humectants, thickeners, electrolyte and salt surfactants, ultraviolet light inhibitors, fixative polymers, preservatives, pigments, dyes, colorants, α hydroxy acids, aesthetic enhancers such as starch fragrances and fragrances, film formers (water repellents), disinfectants, antifungal agents, antimicrobial agents, and other medicaments, and solvents.

Personal care, home care, healthcare and I & I care compositions comprising a segmented core-shell polymer can be formulated at a pH in the range of about 0.5 to about 12. The desired pH of the composition will obviously depend on the particular end product application. Typically, the pH range for personal care applications is from about 3 to about 10 in one aspect, and from about 4.5 to about 10 in another aspect. In another aspect, the segmented core-shell polymer/surfactant composition, when formulated at a pH of about 6 and below, produces a clear formulation while maintaining the desired rheological properties of the composition comprising the same. In yet another aspect, the segmented core-shell/surfactant composition, when formulated at pH values of about 5.0 and lower, results in a clear formulation while maintaining the desired rheological properties of the composition comprising the same.

Generally, depending on the desired end use, the desired pH range for home care applications is from about 1 to about 12 in one aspect, and from about 3 to about 10 in another aspect.

The pH of the compositions disclosed herein can be adjusted using any combination of acidic and/or basic pH adjusting agents known in the art.

Examples of inorganic bases include, but are not limited to, Triethanolamine (TEA), diisopropanolamine, triisopropanolamine, aminomethylpropanol, dodecylamine, cocoamine, oleylamine, morpholine, tripentylamine, triethylamine, tetra (hydroxypropyl) ethylenediamine, L-arginine, aminomethylpropanol, 2-amino-2-hydroxymethyl-1, 3-propanediol, and PEG-15 cocoamine.

Such acidic materials include organic and inorganic acids, such as acetic acid, citric acid, tartaric acid, α -hydroxy acid, β -hydroxy acid, salicylic acid, lactic acid, glycolic acid, and natural fruit acids, or inorganic acids, such as hydrochloric acid, nitric acid, sulfuric acid, sulfamic acid, phosphoric acid, and combinations thereof.

The skilled artisan will recognize that acidic pH adjusting agents may provide more than one function, for example, acidic preservative compounds and acid-based cosmeceutical compounds (e.g., α -hydroxy acids and β -hydroxy acids) not only provide their primary preservative and cosmeceutical functions, respectively, but may also be used to reduce or maintain the pH of the desired formulation.

Buffering agents may be used in the disclosed compositions. Suitable buffering agents include, but are not limited to, alkali or alkaline earth metal carbonates, phosphates, bicarbonates, citrates, borates, acetates, anhydrides, succinates, and the like, such as sodium phosphate, sodium citrate, sodium acetate, sodium bicarbonate, and sodium carbonate.

The pH adjusting agent and/or buffering agent is used in any amount necessary to achieve and/or maintain the desired pH of the composition.

The core-shell polymers disclosed herein may be formulated in the presence or absence of at least one surfactant. Such compositions may comprise any combination of optional additives, adjuvants, and benefit agents suitable for the desired personal care, home care, healthcare, and institutional and industrial care products known in the art. The choice and amount of each optional component used will vary with the purpose and nature of the final product and can be readily determined by those skilled in the formulation art and from the literature. It will be appreciated that various additives, adjuvants, and benefit agents, as well as the components set forth herein, may serve more than one function in the composition, such as surfactants, emulsifiers, solubilizers, conditioning agents, emollients, humectants, lubricants, pH adjusters, and acid-based preservatives.

While selected embodiments and aspects disclosed herein have expressed overlapping weight ranges of the various components and ingredients that may be included in the compositions, it will be apparent that the specific amounts of each component in the disclosed personal care, home care, healthcare, and I & I care compositions will be selected from the ranges disclosed therein, whereby the amount of each component will be adjusted such that the sum of all components in the composition will total 100 weight percent. The amount used will vary with the purpose and nature of the desired product and can be readily determined by those skilled in the formulation art and from the literature.

Optional additives and adjuvants include, but are not limited to, insoluble materials, medicinal and cosmetic pharmaceutical actives, chelating agents, conditioning agents, diluents, solvents, fragrances, humectants, lubricants, solubilizers, emollients, opacifiers, colorants, antidandruff agents, preservatives, coating aids, emulsifiers, sunscreens, immobilizing polymers, botanicals, viscosity modifiers and the like, as well as a variety of other optional components for enhancing and maintaining the properties of desired personal care, home care, healthcare and I & I care compositions.

In one embodiment, the rheology modifier must be neutralized to a pH of 6-6.5 and above with a base to achieve activation. However, some formulations, especially personal care formulations, having a pH value in the range of 4 to 5.5 are required. For such formulations, the rheology modifier composition containing the alkali swellable polymer may be mixed into an aqueous formulation containing a surfactant, activated by neutralization to about pH 6.5 or higher and then acidified in the presence of the surfactant to reduce the formulation pH to 3-6.5, preferably to 4-5.5, according to the acid back titration method described in U.S. patent nos. 4,529,773, 6,635,702, and 6,897,253, the disclosures of each of which are incorporated herein by reference in their entirety.

Some non-limiting examples of polymers that may be used in personal care formulations with the rheology modifier compositions disclosed herein are polyoxyethylated vinyl acetate/crotonic acid copolymers, vinyl acetate crotonic acid (90/10) copolymers, vinyl acetate/crotonic acid/vinyl neodecanoate terpolymers, N-octylacrylamide/methyl acrylate/hydroxypropyl methacrylate/acrylic acid/t-butylaminoethyl methacrylate copolymers, and methyl vinyl ether/maleic anhydride (50/50) copolymers mono-esterified with butanol or ethanol, acrylic acid/ethyl acrylate/N-t-butyl-acrylamide terpolymers, and poly (methacrylic acid/acrylamidomethylpropane sulfonic acid), Acrylate copolymers, octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers, acrylate/octylacrylamide copolymers, VA/crotonate/vinyl neodecanoate copolymers, poly (N-vinylacetamide), poly (N-vinylformamide), modified corn starch, sodium polystyrene sulfonate, polyquaternaries such as polyquaternaries-4, polyquaternaries-7, polyquaternaries-10, polyquaternaries-11, polyquaternaries-16, polyquaternaries-28, polyquaternaries-29, polyquaternaries-46, polyether-1, polyurethane, VA/acrylate/lauryl methacrylate copolymers, adipic acid/dimethylaminopropyl diethylene AMP/acrylate copolymers, methacryloyl ethyl betaine/acrylate copolymers, poly (vinyl acetate/co-vinyl acetate), PVP/dimethylaminoethyl methacrylate copolymer, PVP/DMAPA acrylate copolymer, PVP/vinylcaprolactam/DMAPA acrylate copolymer, vinylcaprolactam/PVP/dimethylaminoethyl methacrylate copolymer, VA/butyl maleate/isobornyl acrylate copolymer, VA/crotonate copolymer, acrylate/acrylamide copolymer, VA/crotonate/vinyl propionate copolymer, vinylpyrrolidone/vinyl acetate/vinyl propionate terpolymer, VA/crotonate, cationic and amphoteric guar gum, polyvinylpyrrolidone (PVP), polyvinylpyrrolidone/vinyl acetate copolymer, PVP acrylate copolymer, vinyl acetate/crotonic acid/vinyl propionate, PVP acrylate copolymer, PVP/vinyl acetate/vinyl propionate, PVP acrylate copolymer, PVP/vinyl acetate/vinyl propionate, PVP/butyl acrylate copolymer, PVP/, Acrylate/acrylamide, acrylate/octylacrylamide, acrylate/hydroxyacrylate copolymers, as well as alkyl esters of polyvinyl methyl ether/maleic anhydride, diethylene glycol/cyclohexanedimethanol/isophthalate/sulfoisophthalate copolymers, vinyl acetate/butyl maleate and isobornyl acrylate copolymers, vinyl caprolactam/PVP/dimethylaminoethyl methacrylate, vinyl acetate/alkyl maleate half ester/N-substituted acrylamide terpolymers, vinyl caprolactam/vinyl pyrrolidone/methacryloylamidopropyl trimethylammonium chloride terpolymers, methacrylate/acrylate copolymers/amine salts, polyvinyl caprolactam, poly (vinyl caprolactam) poly (vinyl pyrrolidone), poly (, Polyurethane, hydroxypropyl guar gum hydroxypropyl trimethylammonium chloride, poly (methacrylic acid/acrylamidomethylpropane sulfonic acid), polyurethane/acrylate copolymers and hydroxypropyl trimethylammonium guar gum chloride, in particular acrylate copolymers, octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers, acrylate/octylacrylamide copolymers, VA/crotonate/vinyl neodecanoate copolymers, poly (N-vinylacetamide), poly (N-vinylformamide), polyurethane, modified corn starch, sodium polystyrene sulfonate, polyquaternium-4, polyquaternium-10 and polyurethane/acrylate copolymers.

Suitable cationic polymers that can be used in formulations comprising the disclosed rheology modifier compositions are those known most preferably as the CTFA class of polyquats. Some examples of such polymers are polyquaternium 6, polyquaternium 7, polyquaternium 10, polyquaternium 11, polyquaternium 16, polyquaternium 22 and polyquaternium 28, polyquaternium 4, polyquaternium 37, quaternium-8, quaternium-14, quaternium-15, quaternium-18, quaternium-22, quaternium-24, quaternium-26, quaternium-27, quaternium-30, quaternium-33, quaternium-53, quaternium-60, quaternium-61, quaternium-72, quaternium-78, quaternium-80, quaternium-81, quaternium-82, quaternium-83 and quaternium-84.

From Amerchol in PolymerCellulose-based polymers of natural origin known from Rhone-Poulenc under the trade nameThe known polyquaternary ammonium 10 or cationic guar gums, as well as guar gum hydroxypropyl trimethylammonium chloride, chitosan, and chitin can also be included in personal care formulations as cationic natural polymers in formulations comprising the disclosed rheology modifier compositions.

Rheology modifiers may be used in personal care compositions, which may also include cosmetically acceptable ingredients. The ingredient may be an emollient, fragrance, exfoliant, drug, whitening agent, acne therapeutic, preservative, vitamin, protein, cleanser or conditioner.

Examples of detergents suitable for use in the compositions herein include, but are not limited to, sodium lauryl sulfate (S L S), sodium laureth sulfate (S L ES), ammonium lauryl ether sulfate (a L ES), alkanolamides, alkyl aryl sulfonates, alkyl aryl sulfonic acids, amine oxides, alkyl benzyl acetate, amines, sulfonated amines and amides, betaines, block polymers, carboxylated alcohol or alkyl phenol ethoxylates, diphenyl sulfonate derivatives, ethoxylated alcohols, ethoxylated alkyl phenols, ethoxylated amines and/or amides, ethoxylated fatty acids, ethoxylated fatty esters and oils, fatty esters (other than glycols, glycerin, etc.), fluorocarbon-based surfactants, glycerol esters, glycol esters, heterocyclic compounds, imidazoline and imidazoline derivatives, hydroxyethyl sulfonates, lanolin-based derivatives, lecithin and lecithin derivatives, lignin and lignin derivatives, methyl esters, monoglycerides and derivatives, olefin sulfonates, phosphate esters, phosphorus-containing organic derivatives, polymers (soaps, acrylic acids, acrylamides), propoxylated and ethoxylated fatty acids, propoxylated and ethoxylated fatty alcohols, propoxylated and ethoxylated alkyl phenol surfactants, protein-based surfactants, alkyl phenol sulfonates, alkyl benzene and phenol sulfates, alkyl benzene sulfonates, sorbitan and phenol sulfates, sorbitan-based derivatives, ethoxylated fatty esters, sorbitan and sorbitan-based fatty esters, fatty alcohol sulfates, sorbitan and sorbitan-based active fatty alcohol sulfates, sorbitan and fatty alcohol sulfates, ethoxylated fatty alcohol and sorbitan derivatives, sorbitan fatty esters, sorbitan esters, and fatty alcohol sulfates, fatty alcohol esters.

In other embodiments, the personal care formulations comprising the disclosed rheology modifiers are hair fixative or styling formulations, such as hair gels, mousses, sprays, creams, waxes, or styling lotions. It has been surprisingly found that some embodiments of the rheology modifiers disclosed herein can be formulated into such hair fixative and styling formulations, thereby resulting not only in the desired rheology modification, but also in hair retention characteristics. When the disclosed rheology modifiers are used in such formulations, other additives conventionally used to provide these functions can be reduced or even eliminated.

In addition to the polymers disclosed herein, the personal care composition may optionally include other ingredients. Some non-limiting examples of such ingredients include, but are not limited to, conditioning agents such as silicone oils, i.e., volatile or non-volatile, natural and synthetic oils. Suitable silicone oils that may be added to the composition include dimethicone, dimethiconol, dimethicone from Dow Corning, silicone oils with various DC fluid ranges. Suitable natural oils may also be used, such as olive oil, almond oil, avocado oil, wheat germ oil, castor oil; and synthetic oils such as mineral oil, isopropyl myristate, palmitate, stearate and isostearate, oleyl oleate, isocetyl stearate, hexyl laurate, dibutyl adipate, dioctyl adipate, myristyl myristate and oleyl erucate. Some examples of nonionic modulators are polyols, such as glycerol, ethylene glycol and derivatives, polyethylene glycol (which may be available under the trade name Union Carbide)PEG and/or from AmercholKnown from the WSR series), polyglycerol, polyethylene glycol mono-or di-fatty acid esters.

Preservatives can be used in personal care formulations to provide long term shelf stability. These preservatives can be selected from methyl paraben, propyl paraben, butyl paraben, DMDM hydantoin, imidazolidinyl urea, glutaraldehyde, phenoxyethanol, benzalkonium chloride (benzalkonium chloride), ammonium methane chloride, benzethonium chloride (benzethonium chloride), benzyl alcohol, chlorobenzyl alcohol, methylchloroisothiazolinone, methylisothiazolinone, sodium benzoate, chloroacetamide, triclosan (triclosan), iodopropynyl butylcarbamate, sodium pyrithione, and zinc pyrithione.

The rheology modifier compositions disclosed herein can also be used in liquid detergent compositions that include one or more surfactants, such as surfactants selected from anionic, nonionic, cationic, amphoteric, and zwitterionic surfactants. In one embodiment, it is preferred that the surfactant is suitable for use in the isotropic liquid detergent composition and is a mixture of anionic and nonionic surfactants, however, it is to be understood that any surfactant can be used alone or in combination with any other surfactant. These liquid detergent systems and surfactants used therein are described in US 6,462,013, which is incorporated herein by reference in its entirety.

Liquid detergent compositions comprising the disclosed rheology modifier compositions may also be used in liquid detergent compositions and may further optionally comprise at least one additive. Suitable additives may include, for example, builders, dispersants, polymers, ion exchangers, bases, anti-corrosion materials, anti-redeposition materials, anti-static agents, optical brighteners, perfumes, fragrances, dyes, fillers, oils, chelants, enzymes, fabric brighteners, sudsing control agents, solvents, solubilizers, bleaching agents, bleach precursors, buffering agents, soil release agents, anti-soiling agents, fabric softeners, and opacifiers. Generally, such additives and amounts thereof are known to those skilled in the art.

Formulation surfactants

In one aspect, a stable aqueous composition comprises a segmented core-shell rheology modifier as disclosed herein and a surfactant. Suitable surfactants include anionic, cationic, amphoteric and nonionic surfactants, and mixtures thereof. Such compositions are useful, for example, in personal care cleansing compositions containing various components such as substantially insoluble materials (e.g., silicones, oily materials, pearlescent materials, aesthetic and cosmetic beads and particles, air bubbles, exfoliants, and the like) that require suspension or stabilization.

Suitable anionic surfactants include, but are not limited to, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkaryl sulfonates, α olefin sulfonates, alkylamide sulfonates, alkaryl polyether sulfates, alkylamido ether sulfates, alkyl monoglycidyl ether sulfates, alkyl monoglyceride sulfonates, alkyl succinates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamido sulfosuccinates, alkyl sulfoacetates, alkyl phosphates, alkyl ether carboxylates, alkylamido ether carboxylates, N-alkyl amino acids, N-acyl amino acids, alkyl peptides, N-acyl taurates, alkyl isethionates, carboxylates where the acyl group is derived from a fatty acid, and alkali metal, alkaline earth metal, ammonium, amine and triethanolamine salts thereof.

In one aspect, the cationic moiety of the foregoing salts is selected from the group consisting of sodium, potassium, magnesium, ammonium, monoethanolamine, diethanolamine, and triethanolamine salts, and monoisopropylamine, diisopropylamine, and triisopropylamine salts. The alkyl and acyl groups of the foregoing surfactants contain from about 6 to about 24 carbon atoms in one aspect, from 8 to 22 carbon atoms in another aspect, and from about 12 to 18 carbon atoms in another aspect, and may be unsaturated. The aryl group in the surfactant is selected from phenyl or benzyl. The above ether containing surfactants may contain from 1 to 10 ethylene oxide and/or propylene oxide units per surfactant molecule in one aspect and from 1 to 3 ethylene oxide units per surfactant molecule in another aspect.

Examples of suitable anionic surfactants include lauryl alcohol ether sulfate, tridecyl alcohol polyether sulfate, myristyl alcohol polyether sulfate, C ethoxylated with 1, 2 and 3 moles of ethylene oxide₁₂-C₁₃Alkanol ether sulfate, C₁₂-C₁₄Alkanol ether sulfates and C₁₂-C₁₅Sodium, potassium, lithium, magnesium and ammonium salts of alkanol ether sulfates; sodium, potassium, lithium, magnesium, ammonium and triethanolamine lauryl sulfate, coco sulfate, tridecyl sulfate, myristyl sulfate, cetyl sulfate, cetearyl sulfate, sodium, potassium, lithium, magnesium, ammonium and triethanolamine lauryl sulfate,Stearyl sulfate, oleyl sulfate and tallow sulfate, disodium lauryl sulfosuccinate, disodium laureth sulfosuccinate, sodium cocoyl isethionate, C₁₂-C₁₄Sodium olefin sulfonates, sodium lauryl alcohol ether-6 carboxylate, sodium methyl cocoyl taurate, sodium cocoyl glycinate, sodium myristyl sarcosinate, sodium dodecylbenzenesulfonate, sodium cocoyl sarcosinate, sodium cocoyl glutamate, potassium myristyl glutamate, triethanolamine monolauryl phosphate and fatty acid soaps, including the sodium, potassium, ammonium and triethanolamine salts of saturated and unsaturated fatty acids containing from about 8 to about 22 carbon atoms.

The cationic surfactant may be any of those known or previously used in the art of aqueous surfactant compositions. Suitable classes of cationic surfactants include, but are not limited to, alkylamines, alkylimidazolines, ethoxylated amines, quaternary ammonium compounds, and quaternized esters. In addition, alkylamine oxides can be used as cationic surfactants at low pH.

The alkylamine surfactant can be substituted or unsubstituted primary, secondary and tertiary fatty C₁₂-C₂₂Salts of alkylamines, and what are sometimes referred to as "amidoamines". Non-limiting examples of alkylamines and salts thereof include dimethylcocoamine, dimethylpalmitylamine, dioctylamine, dimethylstearylamine, dimethylsoyamine, soyamine, myristylamine, tridecylamine, ethylstearylamine, N-tallow propane diamine, ethoxylated stearylamine, dihydroxyethylstearylamine, arachidylsebamide, dimethyllaurylamine, stearylamine hydrochloride, soyamine chloride, stearylamine formate, N-tallow propane diamine dichloride, and amino-terminated dimethylpolysiloxanes (INCI name for silicone polymers and terminated with an amino functional group, such as aminoethylaminopropyl siloxane).

Non-limiting examples of amidoamines and salts thereof include stearamidopropyl dimethylamine, stearamidopropyl dimethylamine citrate, palmitoylamidopropyl diethylamine, and cocamidopropyl dimethylamine lactate.

Non-limiting examples of alkyl imidazoline surfactants include alkyl hydroxyethyl imidazolines, such as stearyl hydroxyethyl imidazoline, coco hydroxyethyl imidazoline, ethyl hydroxymethyl oleyl oxazoline, and the like.

Non-limiting examples of ethoxylated amines include PEG-cocopolyamine, PEG-15 tallow amine, quaternary ammonium salt-52, and the like.

Among the quaternary ammonium compounds useful as cationic surfactants, there are some corresponding to the general formula: (R)⁵R⁶R⁷R⁸N⁺) E- - - -, wherein R⁵、R⁶、R⁷And R⁸Independently selected from aliphatic groups having from 1 to about 22 carbon atoms, or aromatic groups, alkoxy groups, polyoxyalkylene groups, alkylamido groups, hydroxyalkyl groups, aryl groups, or alkylaryl groups having from 1 to about 22 carbon atoms in the alkyl chain; and E- -is a salt-forming anion, such as an anion selected from the group consisting of halogen (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulfate, and alkylsulfate. Aliphatic groups may contain, in addition to carbon and hydrogen atoms, ether linkages, ester linkages, and other groups such as amino groups. The longer chain aliphatic groups, e.g., those having about 12 or more carbons, can be saturated or unsaturated. In one aspect, aryl is selected from phenyl and benzyl.

Exemplary quaternary ammonium surfactants include, but are not limited to, cetyltrimethylammonium chloride, cetylpyridinium chloride, dicetyldimethylammonium chloride, dihexadecyl dimethylammonium chloride, stearyldimethylbenzylammonium chloride, dioctadecyl dimethylammonium chloride, dieicosyl dimethylammonium chloride, dihexadecyl dimethylammonium acetate, behenyltrimethylammonium chloride, benzalkonium chloride, benzethonium chloride and di (cocoalkyl) dimethylammonium chloride, ditallow dimethylammonium chloride, di (hydrogenated tallow) dimethylammonium acetate, ditallow dimethylammonium methyl sulfate, ditallow dipropylammonium phosphate and ditallow dimethylammonium nitrate.

Examples of suitable amine oxide surfactants include, but are not limited to, dimethyl-dodecylamine oxide, oleyl bis (2-hydroxyethyl) amine oxide, dimethyltetradecylamine oxide, bis (2-hydroxyethyl) -tetradecylamine oxide, dimethylhexadecylamine oxide, behenylamine oxide, cocoamine oxide, decyltetradecylamine oxide, dihydroxyethyl C12-15 alkoxypropyl amine oxide, dihydroxyethyl cocoamine oxide, dihydroxyethyl laurylamine oxide, dihydroxyethyl stearylamine oxide, dihydroxyethyl tallow amine oxide, hydrogenated palm kernel amine oxide, hydrogenated tallow amine oxide, hydroxyethyl hydroxypropyl C₁₂-C₁₅Alkoxypropylamine oxide, laurylamine oxide, myristylamine oxide, cetylamine oxide, oleylamidopropylamine oxide, oleylamine oxide, palmitylamine oxide, PEG-3 laurylamine oxide, dimethyllaurylamine oxide, potassium triphosphatidylmethylamine oxide, soya oleylamidopropylamine oxide, cocamidopropylamine oxide, stearylamine oxide, tallow amine oxide and mixtures thereof.

Amphoteric or zwitterionic surfactants are molecules that contain both acidic and basic moieties and are capable of acting as either an acid or a base. Suitable surfactants may be any of the amphoteric surfactants known or previously used in the art of aqueous surfactant compositions. Exemplary amphoteric surfactant classes include, but are not limited to, amino acids (e.g., N-alkyl amino acids and N-acyl amino acids), betaines, sultaines, and alkyl amphocarboxylates.

Suitable amino acid surfactants include surfactants represented by the formula:

wherein R is¹⁰Represents a saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms or an acyl group containing a saturated or unsaturated hydrocarbon group having 9 to 22 carbon atoms, Y is hydrogen or methyl, Z is selected from hydrogen, -CH₃、-CH(CH₃)₂、-CH₂CH(CH₃)₂、-CH(CH₃)CH₂CH₃、-CH₂C₆H₅、-CH₂C₆H₄OH、-CH₂OH、-CH(OH)CH₃、-(CH₂)₄NH₂、-(CH₂)₃NHC(NH)NH₂、-CH₂C(O)O--M⁺、-(CH₂)₂C(O)O--M⁺. M is a salt-forming cation. In one aspect, R¹⁰Represents a linear or branched C₁₀To C₂₂Alkyl, straight-chain or branched C₁₀To C₂₂Alkenyl radical, of¹¹C (O) -a group of acyl group represented by (A) wherein R is¹¹Selected from straight-chain or branched C₉To C₂₂Alkyl, straight-chain or branched C₉To C₂₂An alkenyl group. In one aspect, M⁺Selected from sodium, potassium, ammonium and Triethanolamine (TEA).

Amino acid surfactants may be derived from the alkylation and acylation of α -amino acids such as alanine, arginine, aspartic acid, glutamic acid, glycine, isoleucine, leucine, lysine, phenylalanine, serine, tyrosine, and valine representative N-acyl amino acid surfactants are, but are not limited to, the mono-and di-carboxylic acid salts of N-acylated glutamic acid (e.g., sodium, potassium, ammonium, and TEA), such as sodium cocoyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium palmitoyl glutamate, sodium stearoyl glutamate, disodium cocoyl glutamate, disodium stearoyl glutamate, potassium cocoyl glutamate, potassium lauroyl glutamate, and potassium myristoyl glutamate, the carboxylic acid salts of N-acylated alanine (e.g., sodium, potassium, ammonium, and TEA), such as sodium cocoyl alanine and TEA lauroyl alanine salts, the carboxylic acid salts of N-acylated glycine (e.g., sodium, potassium, ammonium, and ammonium), such as sodium cocoyl glycine and potassium cocoyl glycine, the carboxylic acid salts of N-acylated sarcosinate (e.g., sodium, potassium, TEA, ammonium, and TEA), such as sodium, sodium lauroyl sarcosinate, sodium and ammonium sarcosinate, and mixtures of the foregoing.

The betaines and sultaines useful in the disclosed compositions are selected from the group consisting of alkyl betaines, alkyl amino betaines and alkyl amido betaines represented by the following formulas, and the corresponding sultaines (sultaines):

wherein R is¹²Is C₇-C₂₂Alkyl or alkenyl, each R¹³Independently is C₁-C₄Alkyl radical, R¹⁴Is C₁-C₅Alkylene or hydroxy substituted C₁-C₅Alkylene, n is an integer from 2 to 6, A is carboxylate or sulfonate, and M is a salt-forming cation. In one aspect, R¹²Is C₁₁-C₁₈Alkyl or C₁₁-C₁₈An alkenyl group. In one aspect, R¹³Is methyl. In one aspect, R¹⁴Is methylene, ethylene or hydroxypropyl. In one aspect, n is 3. In another aspect, M is selected from the group consisting of sodium, potassium, magnesium, ammonium, and monoethanolamine, diethanolamine, and triethanolamine cations.

Examples of suitable betaines include, but are not limited to, lauryl betaine, coco betaine, oleyl betaine, coco cetyl dimethyl betaine, lauryl amidopropyl betaine, oleoyl amidopropyl betaine, coco amidopropyl betaine, and coco amidopropyl hydroxysultaine.

Alkyl amphocarboxylates, such as alkyl amphoacetates and alkyl amphopropionates (mono-substituted di-substituted carboxylates) can be represented by the formula:

wherein R is¹²Is C₇-C₂₂Alkyl or alkenyl radicals, R¹⁵is-CH₂C(O)O--M⁺、-CH₂CH₂C(O)O--M⁺or-CH₂CH(OH)CH₂SO₃--M⁺，R¹⁶Is hydrogen or-CH₂C(O)O--M⁺And M is a cation selected from the group consisting of sodium, potassium, magnesium, ammonium, and monoethanolamine, diethanolamine, and triethanolamine.

Exemplary alkyl amphocarboxylates include, but are not limited to, sodium cocoamphoacetate, sodium lauroamphoacetate, sodium caprylocamphodiacetate, disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium octylamphodiacetate, disodium caprylocamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium octylamphodipropionate, and disodium caprylocamphodipropionate.

The nonionic surfactant can be any of those known or previously used in the art of aqueous surfactant compositions. Suitable nonionic surfactants include, but are not limited to, aliphatic (C)₆-C₁₈) Primary or secondary linear or branched acids, alcohols or phenols; an alkyl ethoxylate; alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy moieties); a block alkylene oxide condensate of an alkylphenol; alkylene oxide condensates of alkanols; and ethylene oxide/propylene oxide block copolymers. Other suitable nonionic surfactants include mono-or dialkyl alkanolamides; alkyl Polyglucosides (APG); sorbitan fatty acid esters; polyoxyethylene sorbitan fatty acid esters; polyoxyethylene sorbitol esters; polyoxyethylene acids and polyoxyethylene alcohols. Other examples of suitable nonionic surfactants include cocomonoethanolamide or diethanolamide, cocoglucoside, decyl diglucoside, lauryl diglucoside, cocodiglucoside, polysorbate 20, 40, 60 and 80, ethoxylated straight chain alcohols, cetearyl alcohol, lanolin alcohol, stearic acid, glyceryl stearateEster, PEG-100 stearate, lauryl alcohol ether 7 and oleyl alcohol ether 20.

In another embodiment, nonionic surfactants include, but are not limited to, alkoxylated methyl glucosides, such as methyl gluceth-10, methyl gluceth-20, PPG-10 methyl glucose ether, and PPG-20 methyl glucose ether, each under the trade name PPG-20 methyl glucose etherE10、E20、P10 andp20 is available from L ubrizol Advanced Materials, Inc., and hydrophobically modified alkoxylated methyl glucosides such as PEG120 methyl glucose dioleate, PEG-120 methyl glucose trioleate and PEG-20 methyl glucose sesquistearate, each under the tradename PEG-120 methyl glucose trioleateDOE-120、Glucamate^TML T and Glucamate^TMSSE-20 is available from L ubrizol Advanced Materials, Inc., and is also suitable other exemplary hydrophobically modified alkoxylated methyl glucosides are disclosed in U.S. Pat. Nos. 6,573,375 and 6,727,357, the disclosures of which are incorporated herein by reference in their entirety.

Other surfactants that may be used in the disclosed compositions are described in more detail in WO 99/21530, U.S. patent No. 3,929,678, U.S. patent No. 4,565,647, U.S. patent No. 5,720,964, and U.S. patent No. 5,858,948. In addition, suitable surfactants are also described in McCutcheon's emulsifiers and Detergents (north american and international edition, Schwartz, Perry and Berch), which are hereby incorporated by reference in their entirety.

Although the amount of surfactant used in compositions comprising the disclosed segmented core-shell polymers can vary widely depending on the desired application, typical amounts thereof are generally in the range of from about 1 to about 80 weight percent in one aspect, from about 3 to about 65 weight percent in another aspect, from about 5 to about 30 weight percent in yet another aspect, from about 6 to about 20 weight percent in another aspect, and from about 8 to about 16 weight percent, based on the total weight of the personal care, home care, healthcare, and institutional and industrial care compositions including the surfactant.

In one aspect, the personal care, home care, healthcare, and I & I care compositions disclosed herein comprise a combination of a segmented core-shell polymer and at least one anionic surfactant. In another aspect, the composition comprises a segmented core-shell polymer and at least one anionic surfactant and at least one amphoteric surfactant. In one aspect, the anionic surfactant is selected from alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkaryl polyether sulfates and mixtures thereof, wherein the alkyl group contains from 10 to 18 carbon atoms, the aryl group is a phenyl group, and the ether group contains from 1 to 10 moles of ethylene oxide. Representative anionic surfactants include, but are not limited to, sodium and ammonium lauryl ether sulfate (ethoxylated with 1, 2 and 3 moles of ethylene oxide), sodium, ammonium and triethanolamine lauryl sulfate.

In one aspect, the amphoteric surfactant is selected from the group consisting of alkyl betaines, alkyl amino betaines, alkyl amido betaines, and mixtures thereof. Representative betaines include, but are not limited to, lauryl betaine, coco cetyl dimethyl betaine, cocoamidopropyl hydroxysultaine, and mixtures thereof.

Examples of sulfate-free surfactants include, but are not limited to, ethoxylated alkylphenols, ethoxylated amines and/or amides, ethoxylated fatty acids, ethoxylated fatty esters and oils, fatty esters (other than ethylene glycol, glycerol, etc.), fluorocarbon-based surfactants, glycerol esters, ethylene glycol esters, heterocyclic compounds, imidazolines and imidazolines, isethionates, lanolin-based derivatives, lecithin and lecithin derivatives, lignin and lignin derivatives, methyl esters, monoglycerides and derivatives, phosphate esters, phosphorus-containing organic derivatives, polymers (polysaccharides, acrylic acid, acrylamide), propoxylated and ethoxylated fatty acids, propoxylated and ethoxylated fatty alcohols, propoxylated and ethoxylated alkylphenols, protein-based surfactants, quaternary ammonium surfactants, sarcosine derivatives, polysiloxane-based surfactants, α -olefins, alkyl aryl sulfonates of sulfonic acids, sulfonates of oils and fatty acids, ethoxylated alkyl phenols, cumene, benzene, toluene, or naphthalene sulfonates, and xylene, and their condensation, and their sulfate-free surfactants, such as petroleum sulfonates, naphthalene sulfonates, benzene sulfonates, toluene sulfonates, and naphthalene sulfonates, and their condensation, and their use in the preparation of a shampoo or a cleansing composition.

Some non-limiting examples of sulfated surfactants are sodium lauryl sulfate (S L S), sodium laureth sulfate (S L ES), alkanolamides, alkylarylsulfonic acids, sulfates of oils and fatty acids, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, sulfates of fatty esters, sulfosuccinamates, sulfosuccinates and derivatives thereof.

Examples

The following examples are intended to illustrate various embodiments of the disclosed rheology modifiers and formulations containing these rheology modifiers and are not intended to limit the scope of the appended claims.

In the examples and the attached tables, the following materials and abbreviations are used.

BA-N-butyl acrylate from Arkema, Albama (A L)

EA-Ethyl acrylate from Sasol-Bayonne, N.J. (NJ)

MAA-methacrylic acid available from Evonik-Avondale, Louisiana (L A)

MMA-methyl methacrylate from L kite-Nederland, Tex (TX)

BEI-Wasabosyl ethoxylated itaconate of formula I (B) available from Akzo Nobel Chemicals of North Carolina (NC)

CD 559-alkyl ethoxylated methacrylate of formula I (A) shown above from Akzo Nobel Chemicals, N.C.

S L S-30% sodium lauryl sulfate solution available from Royal Coatings and Specialty Polymers, Indiana (IN)

2-ME-2-mercaptoethanol from Millipore Sigma, Mass

TMPTA-trimethylolpropane triacrylate from Millipore Sigma, Mass

EGDMA-ethylene glycol dimethacrylate purchased from Millipore Sigma, Mass

DAP-diallyl phthalate available from Millipore Sigma, Mass